UNIT OPERATIONS OF CHEMICAL

ENGINEERING II (CHC531)
 Syllabus

Module I: Principles of mass transfer: Introduction, diffusion, classification of diffusion, Inter-phase mass transfer. [8 hr]

Module II: Evaporation: Introduction, types of evaporators, design calculation and processes [8 hr]

Module III: Drying: Principles of drying, drying characteristics, methods, equipment. Humidification and
Dehumidification: Definitions, adiabatic saturation temperature, wet bulb temperature, processes [8 hr]

Module IV: Absorption: Principle, operation and design calculation [8 hr]

Module V: Distillation: Flash distillation, differential distillation, fractionation and design calculations [8 hr]

Module VI: Extraction and Adsorption: Principles and Operations. [8 hr]

Course Outcome

To learn different types of mass transfer phenomena

Understanding the fundamentals of mass transfer operations

To learn design parameters, their effects and calculations

To compare different types of mass transfer operations and their applications

To solve related problems of different difficulty levels through tutorials

Text Books:

1. B.K.Dutta, Principles of Mass Transfer and Separation Processes, Prentice

Hall India Private Limited
2. N Anantharaman and K.M.M.S. Begum, Mass Transfer theory and practice.
Prentice Hall India Private Limited
3. Robert E. Treybal, Mass Transfer Operations, McGraw Hill limited
4. Geankoplis, C. J, Transport process and unit operations, Prentice Hall,3rd
Ed,1993
 Introduction of Mass Transfer

• Almost all chemical processes require a preliminary purification of the raw

materials or separation of products from by products

• Separation of chemical mixture into their constitutions has been practiced for a
long time

Example:

✓ extract perfumes from plant

✓ Dyes from plant
✓ Evaporate sea water to produce the salt
There are many separation methods which are based on entirely mechanical
Example:
• Filtration of solid from suspension in a liquid
• Screening

What is Mass Transfer?

Net movement of a component in a mixture from one location to another location where the component
exists at a different concentration

Common ex: Lump of sugar added to a cup of tea

Agarbati – fragrance spreads throughout uniformly
Drying of cloths under the sun
Industrial ex: Separation of CO2 from the flue gas – absorption
Ethanol and water mixture – distillation
Classification of mass transfer operations

Gas – Liquid – Solid

1. Gas – Gas : Not practically applicable

2. Gas – Liquid: absorption – solute transfer from gas phase to liquid phase ex: ammonia + air - water
3. Gas-Solid - Drying: solute transfer to gas phase
4. Liquid – Liquid : Extraction two immiscible phase brought come in contact
5. Liquid – Solid: Crystallization – formation of solid in liquid based on solute conc, solubility at temp
/ Leaching
6. Solid – Solid: diffusion is slow – not viable
Mechanism of Mass Transfer

• Molecular Mass Transfer – occur by molecular diffusion by virtue of thermal energy

of molecule

• Convective Mass Transfer- macroscopic movement of the fluid

Driving force of Mass Transfer

• True mass transfer driving force is chemical potential

• But single phase deals with concentration as driving force

 Molecular Diffusion

• In molecular diffusion, molecules are

moving from higher concentration to lower
concentration randomly as a result of their
thermal motion. This random movement is
called the Brownian motion

• Difference in centration is the most

common driving force in molecular
diffusion. This is called concentration
gradient

• Concentrations will be equalized over the

time because of the diffusion
Rate of molecular diffusion

How to increase the molecular diffusion

• Increase in Temperature

• Decrease in pressure

Difference between Molecular diffusion and Eddy diffusion

• Eddy diffusion is much faster than molecular diffusion

Concentration
𝑀𝑖
Mass Concentrations for component i: 𝜌𝑖 =
𝑣
𝑛
Total Mass Concentration: 𝜌 = ෍ 𝜌𝑖
𝑖=1

𝜌𝑖𝜌𝑖
Mass Fraction: 𝑤𝑖 = 𝑛 =
σ𝑖=1 𝜌𝑖 𝜌

𝜌
Sum of Mass Fraction : σ𝒏𝒊=𝟏 𝑤𝑖 = σ𝒏
𝒊=𝟏 𝜌
𝑖

𝑷𝒊
Molar Concentrations: Ci =
𝑹𝑻

Total Molar Concentrations: C = σ𝒏𝒊=𝟏 𝐶 𝑖

𝟏 𝑷𝒕
Total Molar Concentrations for ideal gas mixture: 𝑪 = σ𝒏𝒊=𝟏 𝒑 𝒊 =
𝑹𝑻 𝑹𝑻
Mole fraction of component i (Liquid & Solid)
𝐶𝑖
𝑥𝑖 =
𝐶
𝐶𝑖
y𝑖 =
𝐶
𝑃𝑖
=
𝑃𝑡
𝑛 𝑛

෍ 𝑥𝑖 = 1, ෍ 𝑦𝑖 = 1,
𝑖=1 𝑖=1
Calculate the mass concentration of 2 gram moles of sulpher dioxide to be used
to manufacture sulfuric acid in a 0.20 m3 of reactor.

2 moles of sulpher dioxide is equal to 64 x 2g = 128 g

So mass concentration is 128 g/0.20 m3
= 128x 0.001 kg/0.20 m3
= 0.64 kg/m3
A mixture of noble gases [helium, argon, krypton, and xenon] is at a total pressure of 100 kPa
and a temperature of 200 K. If the mixture has equal kmole fractions of each of the gases,
determine: a) The composition of the mixture in terms of mass fractions. b) Total molar
concentration c) The mass density.
(a) Let 100 kmol of the mixture
Molecular weight of helium, argon, krypton (3), and xenon (4) are 4, 40, 83.8 and 131.3 kg/mol respectively.
Moles of each component of the mixture = 25 moles
So total mass of mixture = 25 x 4+ 25x40+25x83.8+25x131.3 = 6477.5 kg
So mass fractions (component mass/ Total mass) are:
Helium = 25x4/6477.5 = 0.015,
Argon = 25x40/6477.5= 0.154,
Krypton = 25x83.8/6477.5 = 0.323 and
Xenon =25x131.3/6477.5 = 0.507
The average molecular weight of the mixture = total mass/100 kmol = 6477.5 kg/100 kmol = 64.775 kg/kmol =
0.064775 kg/mol

(b) Temperature T = 200 K, Pressure P = 100 kPa, R = 8.314 kPa.m3 .kmol-1 .K-1 .
So Total molar concentration, C = P/RT = 60.14 mol/m3 .

(c) Mass density = Total molar concentration (C) x average molecular weight of the mixture = 60.14 mol/m3 x
0.064775 kg/mol = 3.896 kg/m3 .
 Diffusion Velocities

Mass-average velocity: The mass average velocity can be defined in terms of the
mass concentration and the velocity of species i based on fixed axis. It is expressed as

σ𝑛
𝑖=1 𝜌𝑖𝑣 𝑖 𝜌
Vmassavg = σ𝑛
= σ𝑛𝑖=1 𝑖 𝑣𝑖 = σ𝑛𝑖=1 𝑤𝑖𝑣𝑖
𝑖=1 𝜌𝑖 𝜌

vi= absolute velocity of species w.r.t fixed reference frame

wi = mass fraction of species i
Molar average velocity:

The molar average velocity can be expressed by the expression analogous to the mass average
velocity. It can be represented by replacing mass concentration of species i, 𝜌 i with molar
concentration of species i, Ci :

σ𝑛
𝑖=1 𝐶𝑖𝑣 𝑖 𝑛 𝐶𝑖
Vmoleavg = σ𝑛
= σ𝑖=1 𝑣𝑖 = σ𝑛𝑖=1 𝑥𝑖𝑣𝑖
𝑖=1 𝐶𝑖 𝐶

𝑥𝑖 =
𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖
A gas mixture containing (H2 =15% , CO = 30%, CO2 =5% and N2 = 50%)
flows through a tube of 1 inch diameter, at 15 bar total pressure. If the
velocities of the respective components are 0.05 m/s, 0.03 m/s, 0.02 m/s and
0.03 m/s, calculate the mass average and molar average velocities of the
mixture

1 [𝐶1𝑣1+𝐶2𝑣2+𝐶3𝑣3+𝐶4𝑣4]
Vmoleavg = 𝑦1𝑣1 + 𝑦2𝑣2 + 𝑦3𝑣3 + 𝑦4𝑣4
𝐶 =

= 0.15 𝑥 0.05 + 0.30 𝑥 0.03 + 0.05 𝑥 0.02 + 0.50 𝑥 0.03

= 0.0325 𝑚/𝑠

1 [ρ1𝑣1+ρ2𝑣2+ρ3𝑣3+ρ4𝑣4] 𝑦1 𝑀1𝑣1+𝑦2𝑀2𝑣2+𝑦3𝑀3𝑣3+𝑦4𝑀4𝑣4 = 0.014 m/s

Vmassavg =
ρ =
𝑀𝑎𝑣𝑔

𝑀𝑎𝑣𝑔 = 𝑦1 𝑀1 + 𝑦2𝑀2 + 𝑦3𝑀3 + 𝑦4𝑀4 = 0.15 𝑥 2 + 0.30 𝑋 28 + 0.05 𝑋 44 + 0.50𝑋 28 = 24.9

Fluxes
The flux is defined as the rate of transport of species i per unit area in a direction normal to the transport.
- Vector quantity
o fixed
o mass average vel or molar average velocity

The molar flux of species i can be represented as

Ni-mole = Ci vi

Here Ni-molar is the molar flux of species i and vi is the velocity of i with respect to a fixed reference frame.
In the same fashion, a mass flux,
Ni-mass can be represented as Ni -mass = vi ρi

The units of the molar and mass fluxes are moles/m2 .s and mass/m2 .s.
Sometimes it is convenient to interpret the total flux of species i with respect to an arbitrary
reference frame rather than a fixed set of reference frame.

• The molar flux of species i based on molar average velocity Vmoleavg is denoted by Ji-mol which
can be defined as
Ji−mole = 𝐶𝑖 (vi − Vmoleavg)

• Similarly mass flux of species i based on mass average velocity Vmass avg is denoted by Ji-mass which
can be expressed as

Ji−mass = ρ𝑖 (vi − Vmass avg)

 Relation between Fluxes
One can obtained the molar flux of i with respect to the molar average velocity as

Ji−mole = 𝐶𝑖 (vi − Vmoleavg)

Ji−mole = 𝐶𝑖 vi − 𝐶𝑖Vmoleavg

σ𝑛
𝑖=1 𝐶𝑖𝑣 𝑖
Ji−mole = 𝑁 𝑖 − 𝑚𝑜𝑙𝑒 − 𝐶𝑖 σ𝑛
𝑖=1 𝐶𝑖

𝑁 𝑖 − 𝑚𝑜𝑙𝑒 = Ji−mole + 𝑥𝑖 ෍ 𝑁 𝑖 − 𝑚𝑜𝑙𝑒

𝑖=1
One kmole of gas mixture at a total pressure of 250 kPa and 303 K contains 10% CH4,
30% C2H6, and 60% H2 by volume. The absolute velocities of each species are -10 m/s, -5
m/s, and 15 m/s, respectively, all in the direction of the z axis.
a) Determine the molar average velocity for the mixture.
b) Evaluate the four fluxes: JCH4-mol, NCH4-mol.

1 [𝐶1𝑣1+𝐶2𝑣2+𝐶3𝑣3+𝐶4𝑣4]
a) Vmoleavg = 𝑦1𝑣1 + 𝑦2𝑣2 + 𝑦3𝑣3 + 𝑦4𝑣4 = 6.5 𝑚/𝑠
𝐶 =

b) C = P/RT = 250/(8.314*303) = 0.09924 kmol/m3 = 99.24 mol/m3

CCH4 = 0.10*99.24 mol/m3 = 9.924 mol/m3
JCH4−mole = 𝐶𝐶𝐻4 vCH4 −
Vmoleavg =
-163.746 mol/m2

𝑁 𝐶𝐻4 − 𝑚𝑜𝑙𝑒 = JCH4−mole + 𝐶𝐶𝐻4Vmoleavg

= -163.746 + 9.924*6.5 mol/m2 s = -99.24 mol/m2 s
 Diffusion
Molecules of a species move from a region of higher concentration to that of
lower concentration trending to make the concentration in the medium
uniform
✓ Drop of ink released in the water in a glass
✓ Fragrance of a bunch of roses kept on the centre

Two types of diffusion :

(i) Molecular diffusion
(ii) Eddy diffusion
 Fick’s Law

• Basic law of Diffusion

• Enunciated by Adolf Eugen Fick in 1885

The law states that the molar flux of a species relative to an absorber moving with the molar average velocity is
proportional to the concentration gradient of the species

If A diffuses in a binary mixture of A and B

According to Fick’s law , the flux of A is expressed as

𝑑𝐶𝐴
𝐽𝐴 ∝
𝑑𝑧

dCA
JA = −DAB
dz
𝐷𝐴𝐵 𝑖𝑠 𝑡ℎ𝑒 𝑝𝑟𝑜𝑝𝑜𝑟𝑡𝑖𝑜𝑛𝑎𝑙𝑡𝑦 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑐𝑎𝑙𝑙𝑒𝑑 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛 𝐶𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡
• The Fick’s Law expresses the molar flux JA with respect to an observer moving with the molar average
velocity

• In practice , the molar flux NA in a stationary frame of reference is more useful

Molar average velocity
If the concentration of A in a
σ𝑛
𝑖=1 𝐶𝑖𝑣 𝑖
Vmolavg = 𝐶𝐴𝑣𝐴 + 𝐶𝐵𝑣𝐵 𝑁𝐴 + 𝑁𝐵 mixture is small (dilute solution),
σ𝑛
𝑖=1 𝐶𝑖
𝑉𝑚𝑜𝑙𝑎𝑣𝑔 = = the contribution of the bulk flow
𝐶 𝐶
dCA term becomes small too
JA = −DAB = 𝐶𝐴(𝑣𝐴 − 𝑉𝑚𝑜𝑙𝑎𝑣𝑔)
dz
dCA dCA
−DAB = 𝐶𝐴𝑣𝐴 − 𝐶𝐴𝑉𝑚𝑜𝑙𝑎𝑣𝑔 𝑁𝐴 ≈ 𝐽𝐴 = −DAB
dz dz

dCA 𝐶𝐴𝑣𝐴+𝐶𝐵𝑣𝐵
- DAB = 𝑁𝐴 − 𝐶𝐴
dz 𝐶

dCA 𝑁𝐴 + 𝑁𝐵
−DAB = 𝑁𝐴 − 𝐶𝐴
dz 𝐶
𝐶𝐴 dCA
𝑁𝐴 = 𝑁𝐴 + 𝑁𝐵 − DAB
𝐶 dz

Bulk Flow Molecular diffusion

 Relation between mutual diffusivity of species A and B

• If the gas mixture is ideal, the mutual diffusivities of A and B are equal.
𝐶𝐵 dCB
The flux of B in the mixture can be represented by 𝑁𝐵 = 𝑁𝐴 + 𝑁𝐵 𝐶 − DBA dz

𝐶𝐴 dCA
The flux of A in the mixture can be represented by 𝑁𝐴 = 𝑁𝐴 + 𝑁𝐵 − DAB
𝐶 dz

𝐶𝐴 + 𝐶𝐵 dCB dCA
Add above two eqs 𝑁𝐴 + 𝑁𝐵 = 𝑁𝐴 + 𝑁 𝐵 ( ) − DBA − DAB
𝐶 dz dz

dCA dCB
𝑁𝑜𝑡𝑒: 𝐶 = 𝐶𝐴 + 𝐶𝐵 𝑎𝑛𝑑 =−
dz dz

DAB = DBA
Steady state molecular diffusion through a constant area in a binary gas mixture

Diffusion of A through Non diffusing B • Evaporation of a pure liquid (A) is at the bottom of a narrow
tube
• Large amount of inert or non diffusing air (B) is passed over the
top
• Vapour A diffuses through B in the tube
• The boundary at the liquid surface (at the point 1) is
impermeable to B, since B is insoluble in liquid A
• Hence, B cannot diffuse into or away from the surface

• Therefore, NB = 0
Derivation
𝐶𝐴 dCA
𝑁𝐴 = 𝑁𝐴 + 𝑁𝐵 − DAB
𝐶 dz
For gas phase diffusion, above eq written in terms of partial pressure too. If the gas mixture is assumed to behave
ideally, 𝑝𝐴 𝑝
𝐶𝐴 = 𝐶=
𝑅𝑇 𝑅𝑇
𝑝𝐴 DAB dpA
𝑁𝐴 = (𝑁𝐴 + 𝑁𝐵) −
𝑃 𝑅𝑇 dz
The component B being non diffusing, its flux NB =0
𝑝𝐴 DAB dpA
𝑁𝐴 = 𝑁𝐴 −
𝑃 𝑅𝑇 dz
DAB 𝑃 dpA
𝑁𝐴𝑑𝑧 = −
𝑅𝑇 (P − pA)
For diffusion through a constant area at steady state, NA = constant. If diffusion occurs from a point z =0 (where the
partial pressure of A is pA = pA0 ) to the point z = l (where pA = pAl), integration of eq over the “ length l of the diffusion
path’ yields
D 𝑃 pA1 dpA DAB𝑃 (P − pAl)
AB 𝑁
𝑁𝐴 න 𝑑𝑧 = −
𝑙
න 𝐴 =
𝑅𝑇𝑙 ln
0
𝑅𝑇 pA0 (P − pA) (P − pA0)
The total pressure in the medium is uniform

𝑃 = 𝑝𝐴0 + 𝑝𝐵0 = 𝑝𝐴𝑙 + 𝑝𝐵𝑙

𝑝𝐵0 =
𝑃 − 𝑝𝐴0
𝑝𝐵𝑙 =
𝑃 − 𝑝𝐴𝑙

𝑝𝐴0 - 𝑝𝐴𝑙 = 𝑝𝐵𝑙 −

𝑝𝐵0

DAB𝑃 𝑝 − 𝑝
𝑁𝐴 𝐴0 𝐴𝑙 ln pBl
= 𝑅𝑇𝑙
𝑝𝐴0 − 𝑝𝐴𝑙 pB0

DAB𝑃 𝑝 − 𝑝
𝑁𝐴 = 𝐴0 𝐴𝑙
𝑅𝑇𝑙 𝑝 𝑝 𝐵𝑙 − 𝐵0
ln pBl
pB0
p𝐵𝑀 𝑝𝐵𝑙 − 𝑝𝐵0
= ln pBl
DAB𝑃 𝑝 − 𝑝 pB0
𝑁𝐴 = 𝑅𝑇𝑙
𝐴0 𝐴𝑙
𝑝𝐵𝑀 Log mean partial pressure
 Ammonia (A) diffuses through a stagnant layer of air (B ) 1 cm thick, at 25 0C and 1 atm total pressure.
The partial pressures of NH3 on the two sides of the air layer are pA0 = 0.9 atm and pAl = 0.1 atm
respectively. Air is non diffusing.
Calculate (a) the molar flux of NH3, b) the velocities of individual components with respect to a
stationary observer, c) the molar and the mass average velocities of the components and d) the molar
flux of NH3 with respect to an observer moving with the mass average velocity. Given DAB = 0.214 cm2/s.

DAB𝑃 (P − pAl) 0.214 x 1 (1 − 0.1)

𝑁𝐴 = 𝑅𝑇𝑙 ln
= ln = 1.922 𝑥 10 − 5 𝑔𝑚𝑜𝑙/𝑐𝑚2. 𝑠
(P − pA0) 82.1 𝑥 298 𝑥1 (1 − 0.9)
b) and c) substituting NB = 0 (air is non diffusing)
Ni-mole = Ci vi

NA = C V

1
1.922 𝑥 10 − 5 = 82.1 𝑥 298 𝑣
𝑐𝑚
𝑉 = 0.47 (𝑚𝑜𝑙𝑎𝑟 𝑎𝑣𝑔 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦)
𝑠
 0
1 [ρ1𝑣1+ρ2𝑣2] 𝑦𝐴 𝑀𝐴𝑣𝐴+𝑦𝐵𝑀𝐵𝑣𝐵 𝑦𝐴 𝑀𝐴𝑣𝐴 𝑦𝐴 𝑀𝐴𝑣𝐴
Vmassavg =
ρ = = =
𝑀𝑎𝑣𝑔 𝑀𝑎𝑣𝑔 18 2
.

pA0 = 0.9 yA0 = pA0 /p = 0.9/1 = 0.9

Vmolavg = yA0 vA

vA = 0.47/0.9 = 0.522 cm/s

Vmassavg = 0.9 𝑥 17𝑥 0.522 .

= 0 439 𝑐𝑚/𝑠
18 2
.

𝑝𝐴
JA = 𝐶𝐴 vA − Vmassavg = 0.522 − 0.439 = 3.05 𝑋 10 − 6
𝑔𝑚𝑜𝑙
.𝑠
𝑅𝑇 𝑐𝑚2
Equimolar Counter diffusion of A and B

For equimolar counter diffusion of A and B , NA = -NB+

NA +NB = 0

DAB dpA
𝑁𝐴 = −
𝑅𝑇 dz

𝑙
DAB 𝑝𝐴𝑙
𝑁𝐴 න 𝑑𝑧 = − න 𝑑𝑝 𝐴
0 𝑅𝑇 𝑝𝐴 0

DAB (𝑝 𝐴0 − 𝑝 𝐴𝑙)
𝑁𝐴 =
𝑅𝑇𝑙
Ammonia gas (A) is diffusing through a uniform tube 0.10 mm long
containing N2 gas (B) at 1.0132 x 105 Pa pressure and 298 K. At point 1, PA1 =
1.013 x 104 Pa and at point 2, PA2 = 0.507 x 104 Pa. The diffusivity DAB = 0.230
x 10-4 m2/s
Calculate the flux of A and B at steady state

DAB (𝑝 𝐴0 − 𝑝 𝐴𝑙)
𝑁𝐴 =
𝑅𝑇𝑙

𝑁𝐴= 0.47 kg mol A /s.m2

P – pA1 = pB1= 1.0132 x 105 – 1.013 x 104 = 9.119 x 104 Pa

P – pA2 = pB2= 1.0132 x 105 – 0.507 x 104 = 9.625 x 104 Pa

0.23 𝑋 10−4 (9.119 x 104 − 9.625 x 104)

𝑁𝐵 = = - 0.47 kg mol B /s.m2
8.314 𝑋 298𝑋 0.0001
Non equimolar counter diffusion of A and B

• Molecules of A and B diffuse in opposite directions at different molar rates

Ex: oxygen diffuses through a gas film to reach the surface of a jot char particle and the
product is carbon monoxide only

For each mole of O2 (A) diffusing towards the particle, two moles of CO(B) diffuse in
the opposite direction

It is a case of non equimolar counter diffusion , NA = -NB/2

CO2 is diffusing through non diffusing air under steady state conditions at a total
pressure of 1 atm and temperature 300K.The partial pressure of CO2 is 20 kPa at one
point and 5 kPa at other point. The distance between the points is 5 cm. Calculate
the flux of CO2. Given that at 300K and at 1 atm, DCO2-air = 4 x 10-5 m2/s

CO2 is diffusing at steady state through a straight tube of 0.5 m containing N2 at

300K and 1 atm pressure. The partial pressure of CO2 at one end is 15kPa and 5kPa
at the other end. Given that at 300K and 1 atm. DCO2-N2 = 4x 10-5 m2/s. Calculate the
following for steady state equimolar counter diffusion:
a) Molar flow rate of CO2
b) Molar flow rate of N2
 Diffusion through a varying cross sectional area

𝑁𝐴
𝑁𝐴 =
𝐴

Where 𝑁 𝐴 is kg moles of A diffusing per second or kg mol/s. At steady state, 𝑁 𝐴 will be constant but not A
for a varying area.

Diffusion from a sphere:

• Evaporation of a drop of liquid , the evaporation of a ball of naphthalene and the diffusion of nutrients to a spherical like
microorganism in a liquid.
• Sphere of fixed radius r1 m in an infinite gas medium.
• Component (A) at partial pressure pA1 at the surface is diffusing into the surrounding stagnant medium (B), where pA2 = 0
at some large distance away

• Steady state diffusion will be assumed

𝑁𝐴
• The flux NA can be represented by 𝑁𝐴 = where A = cross sectional area , 4пr2 at point r distance from the center of
𝐴
the sphere 𝑁𝐴
𝑁𝐴 =
4пr2
 Since this is the case of A diffusing through stagnant, nondiffusing B, Eq will be used in its differential form

𝑁𝐴 = −
𝐷𝐴𝐵 𝑑𝑝𝐴
𝑁𝐴 = 𝑅𝑇 1 − 𝑝𝐴 𝑑𝑟
4пr2
𝑃

𝑁 𝐴 𝑟2 𝑑𝑟 𝐷𝐴𝐵 𝑝𝐴2 𝑑𝑝𝐴

න =− න 𝑝
4𝜋 𝑟 𝑟2 𝑅𝑇 𝑝 1− 𝐴
1 𝐴1 𝑃

𝑁𝐴 1 1 𝐷𝐴𝐵 𝑃 − 𝑝 𝐴2
( − )= ln
4𝜋 𝑟1 𝑟2 𝑅𝑇 𝑃 − 𝑝 𝐴1
1
𝑟2 ≫ 𝑟1 , ≅0
𝑟2
𝑁𝐴 1 𝐷𝐴𝐵 𝑃 𝑃𝐴1 − 𝑝 𝐴2
= 𝑁 𝐴1 =
4𝜋 𝑟1 2 𝑅𝑇𝑟1 𝑝 𝐵𝑀

This equation can be simplified further. If pA1 is small compared to P (a dilute gas phase), pBM ≅ 𝑃 Also setting
2r1 = D1,diameter and CA1 = pA1/RT
2𝐷𝐴𝐵
𝑁𝐴1 = 𝑐𝐴1 𝑐𝐴2
𝐷1 −
 A sphere of naphthalene having a radius of 2.0 mm is suspended in a large volume of still air
at 318K and 1.01325 x 105 Pa (1 atm). The surface temperature of the naphthalene can be
assumed to be at 318K and its vapor pressure at 318K is 0.555 mm Hg. The DAB of
naphthalene in air at 318K is 6.92 x 10-6 m2/s. Calculate the rate of evaporation of
naphthalene from the surface.
𝑝𝐵1 + 𝑝𝐵2 1.0125 + 1.01325 𝑥105
𝑝𝐵𝑀 = = = 1.0129 𝑥 105 𝑃𝑎
𝑝𝐴1 = 0.555 𝑚𝑚 𝐻𝑔 = 74 𝑃𝑎 2 2

𝐷𝐴𝐵 𝑃 ( 𝑝𝐴1 − 𝑝𝐴2) 6.92 𝑥 10 − 6 𝑥 (1.01325 𝑥 105)(74 − 0)

𝑝𝐵1 = 𝑃 − 𝑝 𝐴1 = 1.01251 𝑥 105 𝑃𝑎 𝑁𝐴1 = =
𝑅𝑇𝑟1𝑝 𝐵𝑀 2
8.314 𝑥 318 𝑥 1000 𝑥(1.0129𝑥105)
𝑝𝐵2 = 𝑃 − 𝑝 𝐴2 = 1.01325 𝑥105
= 9.68 x 10-8 kg mol A /s.m2
Gas phase diffusion coefficient: measurement and prediction
• For many small gas molecules, the values lie between 0.1 cm2/s and 1 cm2/s at atmospheric pressure
and room temperature
• Gas phase diffusivity generally varies with the absolute temperature raised to the power 1.5 to 1.75 and
inversely to the total pressure up to about 10 atm [DAB ∝ T 1.5 to 1.75 ; DAB ∝ (1/P)]
• It depends significantly also on the molecular weight of a species
• Large molecule diffuses slowly compared to a small molecule and also hinders the diffusion of other
molecules
• The diffusivity strongly depends upon the intermolecular forces in a mixture and is also governed by
collisions of the diffusing molecules with others present in the mixture
• The rate of collision increases as the mean free path decreases
• This is favoured at a high pressure and hence the diffusivity of gas decreases with increasing pressure
 Twin bulb method
• Pseudo steady state approximation
If a is the inner cross section of the connecting tube, l
is its length and pA1 and pA2 (pA1 > pA2) are the
partial pressure of A in the bulbs at any time t, the
steady state rate of transport of A from bulb 1 to bulb
2 can be written as
𝑎 𝐷𝐴𝐵 (𝑝𝐴1 − 𝑝𝐴2)
𝑎𝑁𝐴 = = −𝑎𝑁 𝐵
𝑅𝑇𝑙
If CA1 and CA2 are the instantaneous concentrations of A in the bulbs, the rates of change of these concentrations are given
by the following equations:
𝑑𝐶𝐴1 𝑉1 𝑑𝑝𝐴1
−𝑉1 = 𝑎𝑁 𝐴 − = 𝑎𝑁 𝐴
𝑑𝑡 𝑅𝑇 𝑑𝑡
𝑑𝐶𝐴2 𝑉2 𝑑𝑝𝐴2
𝑉2 = 𝑎𝑁 𝐴 = 𝑎𝑁 𝐴
𝑑𝑡 𝑅𝑇 𝑑𝑡
 𝑑 1 1 𝑎𝐷𝐴𝐵 𝑝𝐴1 −
𝑝𝐴2 1 1
− 𝑝 𝑝𝐴2 = 𝑎𝑅𝑇 + 𝑁 = ( + )
𝑑𝑡 𝐴1 − 𝑉1 𝑉2 𝐴 𝑙 𝑉1 𝑉2

𝑑 𝑝𝐴1 − 𝑝𝐴2 𝑎𝐷𝐴𝐵 1 1

− = + 𝑑𝑡
𝑝𝐴1 − 𝑝𝐴2 𝑙 𝑉1 𝑉2

𝑡 = 0 , 𝑝𝐴1 − 𝑝𝐴2 = 𝑃 − 0 = 𝑃
𝑡 = 𝑡 ′ , 𝑝𝐴1 − 𝑝𝐴2 = 𝑝′𝐴1 − 𝑝′𝐴2

𝑃 𝑎𝐷𝐴𝐵 1 1
ln = + 𝑡′
𝑝′𝐴1 −
𝑝′𝐴2 𝑙 𝑉1 𝑉2
Use of the Stefan Tube

• This method is suitable if under the given set of experimental conditions, one of the components is
available as a volatile liquid and the other component (B) is a gas which is not soluble in A.

• The apparatus is very simple

• Let, at any time t, the liquid level be at a distance z from the top of
the vertical tube, pA1 be the partial pressure of A at the liquid
surface and pA2 at that at the top.
• The diffusional flux of A through this distance z is given as
follows
𝐷𝐴𝐵 𝑃(𝑝𝐴1 − 𝑃𝐴2)
𝑁𝐴 =
𝑅𝑇𝑧 𝑃 𝐵𝑀
If the fall in the liquid level is dz in a small time dt, the number of moles of A that
diffuse out is adz (𝜌𝐴/𝑀𝐴)

𝑎 𝑑𝑧 𝜌𝐴 𝑎𝐷𝐴𝐵 𝑃(𝑝𝐴1 − 𝑃𝐴2)

= 𝑎𝑁𝐴 𝑑𝑡 = dt
𝑀𝐴 𝑅𝑇𝑧 𝑃 𝐵𝑀
Here a is the inner cross section of the vertical tube
𝜌𝐴 and MA are the density and molecular weight of A respectively

If at time t = 0, the liquid level is at z0 from the top, and at time t’, the liquid level is
at z’
𝑅𝑇𝑝𝐵𝑀 ρ𝐴 (𝑧 ′ 2 − 𝑧02)
𝐷𝐴𝐵 =
2𝑃𝑀𝐴 𝑝𝐴1 − 𝑃𝐴2 𝑡′
Predictive Equations for the Gas phase Diffusivity

An empirical eq suggested by Fuller, Schettler and Giddings (1966) can predict binary gas
phase diffusivity up to moderate pressure.
 Atomic and diffusion volume

As an example, let us estimate the diffusivity of cyclo-hexane (A) in nitrogen (B) at 15 0C and 1 atm
pressure.

Cyclo hexane (C6H12)

MA = 84 ; MB = 28 T = 150C = 288 K P=1.013 bar

 Molecular diffusion in Liquids
𝐶𝐴 dCA
𝑁𝐴 = 𝑁 𝐴 + 𝑁 𝐵 − DAB - is valid for both gas and liquid phases
𝐶 dz

• Unlike ideal gases, the total molar concentration of a liquid is expected to vary from one point to another

• While integrating above eq for liquid phase diffusion from point 1 to point 2, use of an average total molar
concentration is justified. Putting xA = CA/C
𝜌 dxA
𝑁𝐴 = 𝑁𝐴 + 𝑁 𝐵 𝑥𝐴 − DAB 𝑎𝑣
𝑀 dz
ρ
av = average molar concentration of the liquid
M
a) For the diffusion of A through non diffusion B

b) For equimolar counter diffusion of A and B

 Experimental Determination of Liquid phase Diffusion Coefficient

• Tortuosity factor is the ratio of the average length of the diffusion

path to the thickness of diaphragm

• For diffusion in the liquid phase, particularly at low

concentrations, it is reasonable to neglect the bulk flow term

• The approximate form of Fick’s law is

dCA
NA = −DAB
dz
𝐷𝐴𝐵 (𝐶𝐴1 − 𝐶𝐴2)
𝑁𝐴 = 𝐶𝐴1 > 𝐶𝐴2
𝑙𝜏
• l is the thickness of the diaphragm and l is the effective length of the diffusion path
• If V1 and V2 are the volumes of the solutions in the two cells The diaphragm cell
• CA1 and CA2 are the concentrations at time t
It is not easy to determine the effective porosity and the tortuosity factor of the diaphragm. It is more convenient to
carry out separate measurements for a solute of known diffusion coefficient in the given solvent to calibrate the
cell.
A two compartment diaphragm cell is used to measure the diffusion coefficient of propionic acid in water at 18.5
0C. The cell has a 1.8 mm thick and 3.5 cm diameter glass frit diaphragm. The volume of the two compartments
are 60.2 cm3 and 59.3 cm3 respectively. A calibration experiment is done by filling the large compartment with
0.3 molar aqueous solution of KCl and the smaller compartment with water. Molecular diffusion of the solute
occurs through the pores of the diaphragm. The concentration of KCl reduces to 0.215 molar at the end of 55.2 h
runtime. The diffusivity of KCl is known to be 1.51 x 10-5 cm2/s at the experimental temperature of 18.5 0C.
Calculate the cell constant from these data.
The cell is then thoroughly washed and the larger compartment is filled with 0.4 molar aqueous propionic acid.
The smaller compartment is filled with water as before. At the end of 56.4 h, a sample from the larger
compartment is found to contain 0.32 molar acid. Calculate the diffusivity of propionic acid in water. If the
average porosity of the diaphragm is 0.39, what is the tortuosity of the pores?
Knudsen diffusion

• The movement of molecules in a mixture is governed by molecular velocity as well as collision with other
molecules. Collision of the diffusing molecules with others present in the mixture offers the resistance to
diffusion.
• If gas diffusion occurs in a very fine pore, particularly at a low pressure, the mean free path of the molecules may
be larger than the diameter of the passage. Then collision with the wall becomes much more frequent than
collision with other molecules.
• The rate of diffusional transport of a species is now governed by its molecular velocity, the diameter of the
passage and of course the gradient of concentration or partial pressure. This is called Knudsen diffusion and
becomes important if the pore size is normally below 50 nm.
• Such a situation commonly occurs for intra particle transport in a catalyst containing fine pores.
A simple approach based on the kinetic theory of gases yields the following expression for Knudsen diffusivity.

2
𝐷𝐾 = 𝑟𝑣
3 𝑝 𝑡
Where rp = radius of the passage or capillary
T = temperature, in K
M = molecular weight

8𝑅𝑇 1/2
𝑣𝑡 = ( ) = average velocity of the molecules
𝜋𝑀

The equation for flux due to Knudsen diffusion is similar to that of Fick’s law

𝑑𝐶𝐴 𝐷𝐾 𝑑𝑝𝐴
𝐽𝐾 = −𝐷𝐾 =−
𝑑𝑧 𝑅𝑇 𝑑𝑧
Estimate the Knudsen diffusivity of ethylene within a 100A pore of a catalyst at 600 K.

2 8𝑅𝑇 1/2
𝐷𝐾 = 𝑟𝑝( )
3 𝜋𝑀

= 0.045 cm2/s
Surface diffusion
• Surface diffusion is the transport of adsorbed molecules on a surface in the presence of a concentration
gradient.
• Molecules adsorbed on a surface remain anchored to the active sites. If the fractional surface coverage is
less than unity, some of the active sites remain vacant
• An adsorbed molecule tends to migrate to an adjacent empty site if it has sufficient energy to jump the
energy barrier.
• Since the active sites are discrete, the migration or surface diffusion is visualized to occur by a hopping or
leap frog mechanism.

𝑑𝐶𝑠
𝐽𝑠 = −𝐷𝑠
𝑑𝑧

The experimental values of DS normally range between 10-4 and 10-5 cm2/s
Self diffusion

• The molecules of a gas or a liquid continuously move from one position to another. As a result of this
continual motion, the molecules in a mixture of uniform composition also diffuse but the net rate of
transport across any plane over a microscope time scale is zero.
• Self diffusion refers to the diffusion of the molecules in a pure substance; the corresponding diffusion
coefficient is called the self diffusion coefficient.
Calculate the rate of diffusion of acetic acid (A) across a film of non diffusing water (B) solution 1 mm
thick at 17 0C when the concentrations on opposite sides of the film are, respectively, 9 and 3 wt% acid.
The diffusivity of acetic acid in the solution is 0.95 x 10-9 m2/s. Density of 9% solution is 1012 kg/m3.
Density of 3% solution is 1003 kg/m3

0.09
𝑥𝐴0 = 60.03 = 0.0288 mole fraction acetic acid
0.09 0.91
60.03 + 18.02

𝑥𝐵0 = 1 − 0.0288 = 0.9712 𝑚𝑜𝑙𝑒𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑤𝑎𝑡𝑒𝑟

0.09 0.91
M= 1/ (60.03 + 18.02)= 19.21 kg/kmol

𝜌 1012
= = 52.7 𝑘𝑚𝑜𝑙/𝑚3
𝑀 19.21
𝜌
For 3% solution xAl = 0.0092 xBl = 0.9908 M = 18.40 = 54.5 𝑘𝑚𝑜𝑙/𝑚3
𝑀
𝜌
𝑎𝑣𝑔 = 53.6 𝑘𝑚𝑜𝑙/𝑚3
𝑀

𝑥𝐵𝑀 = 0.980

𝑘𝑚𝑜𝑙
𝑁𝐴 = 1.018 𝑋 10 − 6 . .
𝑚2 𝑠
Prediction of diffusivities in liquids

• Stokes law was used to describe the drag on the moving solute molecule

• The equation was modified by assuming that all molecules are alike and arranged in a cubic lattice and by
expressing the molecular radius in terms of the molar volume.

9.96 𝑥 10 − 6 𝑇
𝐷𝐴𝐵 = /
𝜇𝑉1 3 𝐴

• Above equation is applies very well to very large unhydrated and spherical like solute molecules of about 1000
molecular weight or greater or where the VA is above about 0.500 m3/ kg mol in aqueous solution
• For smaller solute molar volumes, above eq does not hold. The Wilke Chang corelation can be used for most
general purposes where the solute (A) in dilute in the solvent (B).

φ = association parameter = 2.6 for water

Predict the diffusion coefficient of acetone in water at 250C and 50 0C using Wilke Chang equation. The
experimental value is 1.28 x 10-9 m2/s at 25 0C. Viscosity of water at 25 0C is 0.89 x 10-3 Pa.s. Viscosity of
water at 50 0C is 0.54 x 10-3 Pa.s

For 25 0C DAB = 1.277 x 10-9 m2/s

For 50 0C DAB = 2.251 x 10-9 m2/s

Diffusion in Tapered Tube

Rate of input of A into the section at z = (𝜋𝑟 2 ) NA|Z

Rate of output of A from the thin section at z+∆z = (𝜋𝑟 2 ) NA|Z + ∆𝑧

There is no accumulation within the section at steady state

(𝜋𝑟 2 ) NA|Z − (𝜋𝑟 2 ) NA|Z + ∆𝑧 =0

Dividing by ∆z throughout and taking the limit ∆z → 0,

(𝜋𝑟 2 ) NA|Z − (𝜋𝑟 2 ) NA|Z + ∆𝑧

lim =0 𝑑
∆z →0 ∆z − (𝜋𝑟 2 NA) = 0 𝜋𝑟 2 NA = W1
𝑑𝑧
 𝐷𝐴𝐵 𝑑𝑝𝐴
𝑁𝐴 = −
𝑅𝑇 𝑑𝑧

𝐷𝐴𝐵 𝑑𝑝𝐴
− 𝜋𝑟 2 = W1
𝑅𝑇 𝑑𝑧
The local radius r can be related to the axial position z by using the property of similar triangles
𝑟2 − 𝑟1
𝑟 = 𝑟1 + 𝑧
𝐿
z = 0 pA = pA1
z = L pA = pA2
𝑝𝐴2
W1 𝑅𝑇 𝐿 𝑑𝑧
−න 𝑑𝑝 𝐴 = න
𝑝𝐴1 𝜋𝐷𝐴𝐵 0 𝑟 + 𝑟2 − 𝑟1 𝑧
1 𝐿

𝜋𝐷𝐴𝐵 𝑟1 𝑟2(𝑝𝐴1 − 𝑝𝐴2)

W1 =
𝑅𝑇𝐿
HOME WORK

An ethanol (A)-water (B) solution in the form of a stagnant film 2.0 mm thick at 293 K is in contact at one
surface with an organic solvent in which ethanol is soluble and water is insoluble. Hence, NB =0 . At point 1
the concentration of ethanol is 16.8 wt% and the solution density is 𝜌1 = 972.8 𝑘𝑔/𝑚3. At point 2 the
concentration of ethanol is 6.8 wt% and 𝜌2 = 988.1 𝑘𝑔/𝑚3. The diffusivity of ethanol is 0.740 x 10-9 m2/s.
Calculate the steady state flux NA.

Ans: 8.99 x 10-7 kg mol/s.m2

 Steady state diffusion in multicomponent mixtures
NA +NB = 0 is replaced by σ𝑛𝑖=𝐴 𝑁 𝑖 ,

where Ni is positive if diffusion is in the same direction as that of A and negative of in the opposite
direction and DAB is replace by the effective DA, m

𝑛
𝑁𝐴 − 𝑦𝐴 ‫𝑖𝑁 𝐴=𝑖׬‬
𝐷 𝐴, 𝑚 =
1
σ𝑛𝑖=𝐴 (𝑦 𝑁 − 𝑦𝐴 𝑁𝑖 )
𝐷𝐴𝑖 𝑖 𝐴

If all N’s except NA are zero; such as all but one component is stagnant, eqs becomes

1 − 𝑦𝐴 1
𝐷 𝐴, 𝑚 = 𝑦𝑖 = 𝑛 𝑦𝑖′
𝑛
σ𝑖=𝐵 σ𝑖=𝐵
𝐷𝐴, 𝑖 𝐷𝐴, 𝑖
 Calculate the rate of diffusion of oxygen (A) , assuming that the non diffusing gas is a mixture of methane (B)
and hydrogen (C) in the volume ratio 2:1. The diffusivities are estimated to be DO2-H2 = 6.99 X 10-5 , DO2-CH4 =
1.86 X 10-5 m2/s. Total pressure is 1 x 105 N/m2 and the temperature 00C. The partial pressure of oxygen at two
planes 2.0 mm apart is, respectively, 13000 and 6500 N/m2. The diffusivity for the mixture is 1.87 x 10-5 m2/s.

Solution: P = 105 N/m2 , T = 273 K, pA1 = 13 x 103 , pA2 = 6500, pbm = 90.2 x 103 yB’ = 2/(2+1) =0.667 yc’ = 1-
0.667= 0.333

1 1
𝐷𝐴,𝑚 = = = 2.46 x10 − 5 m2/s
𝑦𝐵′ 𝑦𝑐′ 0.667 0.333
+
𝐷𝐴𝐵 + 𝐷𝐴𝑐 1.86 𝑥 10 − 5 6.99𝑥 10 − 5

NA = 3.91 X 10-5 kmol/m2.s