Molecular Diffusion

in fluids

Dr. P. A. Joshi Prof. J.M.Jivani

Professor, Dept .of Chem. Engg. Asst. Professor, Dept .of Chem. Engg.
Faculty of Technology Faculty of Technology
Dharmsinh Desai University, Nadiad
Dharmsinh Desai University, Nadiad
 Course Outline
1. What is Diffusion
2. Types of Diffusion
3. Molecular Diffusion
4. Steady-state Molecular Diffusion in Fluids at
Rest or in Laminar Flow
5. Momentum & Heat Transfer

7/29/2021 Dr P A Joshi, DDU, Nadiad 2

 What is Diffusion??
1)The net movement of particles
2)from a region of higher concentration
3)to a region of lower concentration,
4)down the concentration gradient.

High concentration Low concentration

7/29/2021 3
 Diffusion in liquid state

: Ink dye

: Water
molecules

7/29/2021 4
 Diffusion in liquid state

: Ink dye

: Water
molecules

7/29/2021 5
 Diffusion in gaseous state

: Perfume
molecules
: Air
molecules
7/29/2021 6
 Diffusion in gaseous state

: Perfume
molecules
: Air
molecules
7/29/2021 7
 Net Movement

Note: This barrier

does not illustrate a
partially permeable
membrane.

7/29/2021 8
 Net Movement

7/29/2021 9
 Equilibrium
When particles reaches an equilibrium, does the
particles stop moving?

Particles move in a random and dynamic motion.

7/29/2021 10
 Concentration Gradient
The concentration difference between regions of high
concentration and low concentration.
High concentration
gradient

Down the
concentration gradient

Low
concentration
gradient

7/29/2021 11
 Concentration Gradient
Which slide will allow you to go down faster?

Obviously-A
7/29/2021 12
 Concentration Gradient
The steeper the concentration gradient, the faster diffusion takes place

Steeper concentration gradient

Fast rate of
diffusion

Less steep concentration gradient

Slow rate of diffusion

7/29/2021 13
 Types of Diffusion
1) Molecular Diffusion
2) Eddy Diffusion or turbulent diffusion

7/29/2021 14
 Course Outline
1. What is Diffusion
2. Types of Diffusion
3. Molecular Diffusion
4. Steady-state Molecular Diffusion in Fluids at
Rest or in Laminar Flow
5. Momentum & Heat Transfer

7/29/2021 Dr P A Joshi, DDU, Nadiad 15

7/29/2021 16
 Molecular Diffusion
• Diffusion of particles (e.g. molecules of a
substance) by random motion due to
molecular kinetic energy
• Molecular movement is random and travel in
a direction at a specific velocity till collision
with other molecule take place and then
change both direction and speed.
– The number of collisions depend on Pressure.
• The avg distance traverse by a molecule
between collisions is its mean free path and
the velocity depends on the temperature.
• Thus the rate of molecular diffusion is very
small and depends on
– system temperature and pressure

7/29/2021 17
 Molecular Diffusion
Effect of Barrier on Mass Transfer
• Significance of Barrier causing collision: Rate of evaporation of
water at 25 oC under complete vacuum is estimated to be
3.3kg/sq.m-S. By adding 0.1mm thick stagnant air barrier at 1
atm reduces the rate by a factor of 600.
• As compared to molecular diffusion, convective diffusion rate
is much higher.
– A tan k of 1.5m dia and height if is filled half with saturated brine and
half with pure water and allowed diffusion to take place, 10 years will
be required to reach 87.5% uniform concentration and 28 years to
have 99%. However, a simple peddle type agitator rotating at 22 rpm
will need 60 seconds to have complete uniformity because of eddy or
turbulent diffusion.

7/29/2021 18
 Molecular Diffusion
• To describing this quantitatively , we need an
appropriate measure of rate
– Rates will describe in flux or molar flux [ mol/(area) (time) ]
• What Is molar Flux? (Type of flux)
• Flux = Function of velocity (or Diffusion velocity)
• Fick’s first law gives idea about
– Rate of diffusion or
– Flux

7/29/2021 19
 Molecular Diffusion
Fick’s First law
• Rate of mass transfer is given in terms of Molar Flux,
mole/(area)(time), area is measured perpendicular to the
path of diffusion
• We use two types of fluxes,
• NA, the flux relative to fixed position in space which is
important for designing MT equipment and
• JA, the flux of A relative to avg. molar velocity of all
constituents, a Characteristic of constituent.
• Fick’s proposed the flux as
dC dC
Jm   Jm   Dm
dx dx
Jm: flux kmol/sq.m-s
Dm: coefficient of molecular diffusion, sq.m/s
C: concentration kmol/cu.m
x: distance in the direction of net diffusion, m
7/29/2021 20
Diffusion in binary solutions-Relation Between NA & JA

7/29/2021 21
 Diffusion in binary solutions
Looking at the phenomena in the box, we can realize that the quantity on the right
side is Increased due to molecular diffusion of A & B. The net flux of A on the right
is because of the net movement of A from left to right and due to

Here N= NA+NB

7/29/2021 22
 Course Outline
1. What is Diffusion
2. Types of Diffusion
3. Molecular Diffusion
4. Steady-state Molecular Diffusion in Fluids at
Rest or in Laminar Flow
a. Molecular Diffusion in Gases
b. Relation Between NA and NB
c. Situations Encountered
5. Momentum & Heat Transfer

7/29/2021 Dr P A Joshi, DDU, Nadiad 23

 Steady-state Molecular Diffusion in Fluids at
Rest or in Laminar Flow

On integration from location 1 to location 2,we get

--(2.21)

--(2.22)

7/29/2021 24
 Molecular Diffusion in Gases

Eq. 2.22 becomes

7/29/2021 25
 Relation Between NA and NB

7/29/2021 26
 Situations Encountered
• Steady State
• Unsteady state
• Diffusion In Gases
• Diffusion in Liquids
• Unimolecular Diffusion
– Steady state Unimolecular Diffusion
• Equimolar Diffusion
– Steady state Equimolar Diffusion

7/29/2021 27
 Unimolecular Diffusion
NA=Constant & NB=0
• Diffusivity of gas can be measured in an
Arnold diffusion cell

7/29/2021 28
Steady State Diffusion of A through Non-
diffusing B, i.e, NA=Const, NB=0

7/29/2021 29
 Steady State Diffusion of A through Non-
diffusing B

7/29/2021 30
 Situations Encountered
• Steady State
• Unsteady state
• Diffusion In Gases
• Diffusion in Liquids
• Unimolecular Diffusion
• Equimolar Diffusion
– Steady state Equimolar Diffusion

7/29/2021 31
 Equimolar Counter diffusion
NA = - NB
• Flux of one gaseous component is equal to
but in the opposite direction of the second
gaseous component
• Again, for steady-state, no reaction, in the
z-direction, d
N A, z  0
dz
• the molar flux is
 y A N A, z  N B , z 
dc A
N A, z   DAB
dz
7/29/2021 32
 • In equimolar counterdiffusion, NA,z = -NB,z
dc A
N A, z   DAB
dz
Integrated at z = z1, cA = cA1 and at z = z2, cA = cA2
to:
D AB
N A, z  (c A1  c A2 )
( z2  z1 )
• Or in terms of partial pressure,
DAB
N A, z  ( p A1  p A2 )
RT ( z2  z1 )
7/29/2021 33
 Steady-State Equimolar Counter Diffusion
NA = -NB
Such situation is generally encountered in distillation, where
one component from liquid phase diffuses into vapor and
another from vapor into liquid phase

7/29/2021 34
 Steady-State Equimolar Counter
Diffusion

7/29/2021 35
 Situations Encountered
• Steady State
• Unsteady state
• Diffusion In Gases
• Diffusion in Liquids
• Unimolecular Diffusion
• Equimolar Diffusion
– Steady state Equimolar Diffusion

7/29/2021 36
 Molecular Diffusion in Liquids:

• Equation derived for diffusion in gases equally

applies to diffusion in liquids with some
modifications.
• Mole fraction in liquid phases is normally
written as ‘x’ (in gases as y).
• The concentration term ‘C’ is replaced by
average molar density,

7/29/2021 37
7/29/2021 38
 Molecular Diffusion in Liquids

• In case of liquids, the DAB and C both are varying

and hence average values are used with Eq 2.22

Where and M are the solution density and

molecular weight.

7/29/2021 39
 Molecular Diffusion in Liquids
a) Steady State Unimolecular Diffusion

7/29/2021 40
 Course Outline
1. What is Diffusion
2. Types of Diffusion
3. Molecular Diffusion
4. Steady-state Molecular Diffusion in Fluids at
Rest or in Laminar Flow
a. Molecular Diffusion in Gases
b. Relation Between NA and NB
c. Situations Encountered
5. Diffusivity
6. Momentum & Heat Transfer
7/29/2021 Dr P A Joshi, DDU, Nadiad 41
Coefficient of Molecular Diffusion
• DA = f(solvent, solute, temperature)
Carrying Fluid Solute DA(cm2/s)
H2O O2 2.4x10-5
H2O NaCl 1.545x10-5
H2O C6H12O6 0.673x10-5
Air H2 0.634
Air O2 0.178
Air C O2 0.139
Gas molecules have much more kinetic energy (higher
velocity) and greater distance between molecules and thus
diffusion in air is higher than diffusion in water.
7/29/2021 42
 Diffusivity of Gases
Wilke-Lee modification of Herschfelder-Bird-Spotz
For nonpolar gases or a polar and nonpolar gas

7/29/2021 43
7/29/2021 44
 Diffusivity in Gases:
Pressure dependence of diffusivity is given by

(for moderate ranges of pressures,

upto 25 atm).
• And temperature dependency is according to

7/29/2021 45
 Diffusivity in Liquids
Wilke-Chang equation for estimation of liquid diffusivity

7/29/2021 46
 Factors that affects the rate of diffusion
• Cross-sectional area through which diffusion occurs
• Temperature
• Molecular weight of a substance
• Distance through which diffusion occurs

General range of values of diffusivity:

Gases : 5 X 10 –6 ------------- 1 X 10-5 m2 / sec.
• Liquids : 10 –6 ------------- 10-9 m2 / sec.
• Solids : 5 X 10 –14 ------------- 1 X 10-10 m2 / sec.
•

7/29/2021 47
 Equation of Continuity- Fick’s Second Law

---(2.18)

7/29/2021 48
 Course Outline
1. What is Diffusion
2. Types of Diffusion
3. Molecular Diffusion
4. Steady-state Molecular Diffusion in Fluids at
Rest or in Laminar Flow
a. Molecular Diffusion in Gases
b. Relation Between NA and NB
c. Situations Encountered
5. Momentum & Heat Transfer

7/29/2021 Dr P A Joshi, DDU, Nadiad 49

 Momentum Transfer
Momentum Transfer: When a fluid is flowing past a solid surface, the
velocity at the surface is zero and increases gradually at increased
distance from solid. The force per unit area required to maintain
velocity, Shear stress is proportional to velocity gradient

7/29/2021 50
 Momentum & Heat Transfer

Eq.2.48 can be looked upon as momentum transfer rate and kinematic

viscosity as the momentum diffusivity with unit same as mass
Diffusivity, m2/s. The kinetic theory of gases suggests that

Where w is the avg molecular velocity and is the mean free path
Schmidt number, Sc, the ratio of momentum to mass diffusivity is
Unity as per kinetic theory of gases. Actual values are near by and for
liquids the values are much higher, i.e. for self diffusion of
water=296
7/29/2021 51
 Flow past a solid surface

7/29/2021 52
 Heat Transfer in Laminar Flow
• When a temperature gradient exists between solid
surface and the fluid, the rate of heat transfer in
laminar region is given by

The quantity is thermal concentration and

Is thermal diffusivity with m2/s as the units. A simplified kinetic
Theory of gases gives

7/29/2021 53
 Mass, Momentum & Heat Transfer

Under simplified conditions, the mass, momentum and heat transfer

Show analogues behavior. Modifications are required when
Simultaneous mass and momentum transfer takes place.

7/29/2021 54
Examples
 Illustration Example-1

7/29/2021 56
 Example-2
A mixture of He and N2 gas is contained in a
pipe at 298 K and 1 atm total pressure which
is constant throughout. At one end of the pipe
at point 1 the partial pressure pA1 of He is 0.6
atm and at the other end 0.2 m pA2 = 0.2 atm.
Calculate the flux of He at steady state if DAB
of the He-N2 mixture is 0.687 x 10-4 m2/s.

7/29/2021 57
 Solution
• Since a total pressure P is constant, the c is constant, where c is as follows
for a gas according to the perfect gas law:

• Where n is kg mol A plus B, V is volume in m3, T is temperature in K, R is

8314.3 m3.Pa/kg mol.K or R is 82.057 x 10-3 cm3. atm/g. mol. K, and c is kg
mol A plus B/m3.
• For steady state the flux J*Az in Eq.(6.1-3) is constant. Also DAB for gas is
constant. Rearranging Eq. (6.1-3) and integrating.

7/29/2021 (6.1-11) 58
• Also, from the perfect gas law, pAV=nART, and

• Substituting Eq. (6.1-12) into (6.1-11),

(6.1-13)

• This is the final equation to use, which is in a form eqsily used for gases.
Partial pressures are pA1 = 0.6 atm = 0.6 x 1.01325 x 105 = 6.04 x 104 Pa and
pA2 = 0.2 atm = 0.2 x 1.01325 x 105 = 2.027 x 104 Pa. Then, using SI units,

7/29/2021 59
• If pressures in atm are used with SI unit,

• Other driving forces (besides concentration

differences) for diffusion also occur because of
temperature, pressure, electrical potential, and other
gradients.

7/29/2021 60
 Example-3
• Ammonia gas (A) is diffusing through a uniform tube
0.10 m 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.
(a) Calculate the flux J*A at steady state
(b) Repeat for J*B

7/29/2021 61
 Example-4
Water in the bottom of a narrow metal tube is held at a constant
temperature of 293 K. The total pressure of air (assumed dry)
is 1.01325 x 105 Pa (1.0 atm) and the temperature is 293 K (20
°C). Water evaporates and diffuses through the air in the
tube, and the diffusion path z2-z1 is 0.1524 m (0.5 ft) long.
Calculate the rate of evaporation at steady state in lb
mol/h.ft2 and kg mol/s.m2. The diffusivity of water vapor at
293 K and 1 am pressure is 0.250 x 10-4 m2/s. Assume that the
system is isothermal. Use SI and English units.

7/29/2021 62
 Assignment
At one point in the column, the vapour contains 70 mol% benzene and
the adjacent liquid reflux contains 59 mol% benzene. The temperature at
this point is 365 K. Assuming the diffusional resistance to vapour transfer
to be equivalent to the diffusional resistance of a stagnant vapour layer
0.2 mm thick, calculate the rate of interchange of benzene and toluene
between vapour and liquid. The molar latent heats of the two materials
can be taken as equal. The vapour pressure of toluene at 365 K is 54.0
kN/m2 and the diffusivity of the vapours is 0.051 cm2/s.
• Hint: Equimolar counter diffusion, z=0.2mm, As the vapour pressure
of toluene = 54 kN/m2, the partial pressure of toluene PA1from
Raoult’s law = (1- 0.59) x54 = 22.14 kN/m2 and PA2= (1-0.7) x101.3 =
30.39kN/m2
NA

7/29/2021 63
 Assignment-1 Gas-Gas System

Ammonia gas is diffusing at a constant rate through a

layer of stagnant air 1 mm thick. Conditions are such
that the gas contains 50 per cent by volume ammonia at
one boundary of the stagnant layer. The ammonia
diffusing to the other boundary is quickly absorbed and
the concentration is negligible at that plane. The
temperature is 295 K and the pressure atmospheric, and
under these conditions the diffusivity of ammonia in
air is 1.8 x 10~5 m2/s. Estimate the rate of diffusion of
ammonia through the layer.
7/29/2021 64
 Assignment-2: Gas-Gas System
A large tank having gases A (90 mole %) and B is
connected to another large tank with A (5 mole
%) and B. Both the tanks are at 298 K and 1 atm
and are connected through a pipe 5 cm in inner
diameter and 15 cm long. If the rate of transport
of A is found to be 1.95X10-6 kmol/s and
equimolar counter diffusion is prevailing,
calculate the diffusivity of A in B.

7/29/2021 65
 Assignment-3: Gas-Gas System
Water in the bottom of a narrow metal tube is held
at a constant temperature of 293 K. The total
pressure of the dry air is 1.013X105 Pa. Water
evaporates and diffuses through the air in the tube
along a diffusional path of length 0.1524 m.
Calculate the rate of evaporation at steady state if
diffusivity at given condition is 0.25X10-4 m2/s and
the vapor pressure of water at 293 K is 2.34X103 Pa.
Also find the partial pressure of water vapor at a
distance of 0.07 m form the interface.

7/29/2021 66
 Assignment-4: Gas-Gas System
• Methane diffuses at steady state through a
tube containing helium. At two planes 0.03m
apart the partial pressure of methane is 100
kPa and 30 kPa, respectively. The total
pressure is 202.62 kPa and temperature is 303
K. If the molar flux of methane is 5.2X10-5
kmol/m2s, calculate the diffusivity at 293 K
and 1 atm pressure.

7/29/2021 67
 Example
As shown in Figure 2, an open beaker, 6 cm in height, is filled
with liquid benzene at 25°C to within 0.5 cm of the top. A
gentle breeze of dry air at 25°C and 1 atm is blown by a fan
across the mouth of the beaker so that evaporated benzene is
carried away by convection after it transfers through a
stagnant air layer in the beaker. The vapor pressure of
benzene at 25°C is 0.131 atm. The mutual diffusion coefficient
for benzene in air at 25°C and 1 atm is 0.0905 cm2/s.
Compute:
(a) The initial rate of evaporation of benzene as a molar flux in
mol/cm2.s
(b) The time required for evaporation of 10% of benzene if the
diameter of the beaker is 5 cm. Density of benzene at 25°C is
870 kg/cu.m
7/29/2021 68
 Evaporation of Benzene in Air

7/29/2021 69
 Illustration
Calculate the rate of diffusion of Acetic acid (A)
across a film of non-diffusing water (B) solution of 1
mm thick at 17 oC. The concentrations of acid on
the opposite sides of the film are 9 wt% and 3 wt%
respectively. Given that the diffusivity of Acetic acid
in the solution is 0.95*10-9 m2/s at 17 oC and the
specific gravity of pure Acetic acid is 1.049. The
molecular weight of Acetic acid is 60 and for water
is 18.

7/29/2021 70
 On assumption of 1kg total solution

7/29/2021 71
 Assignment-1: Liquid-Liquid System

• At the bottom of a cylindrical container is n-butanol.

Pure air is passed over the open top of the container.
The pressure is 1 atm and the temperature is 70 °F. The
diffusivity of air-n-butanol is 8.57×10‒6 m2/s at the
given conditions. If the surface of n-butanol is 6.0 ft
below the top f the container, calculate the diffusion
rate of n-butanol. Vapor pressure of n-butanol is 0.009
atm at the given conditions.
• [Universal gas constant = 0.08205 m3-atm/kmol-K]

7/29/2021 72
 Assignment-2: Liquid-Liquid System
Hydrochloric acid (A) diffuses through 4
mm thick stagnant film of water (B) at 298 K.
The concentration of A on the two opposite
sides of the film is 12 wt % (sp.gr. 1.06) and 4 wt
% (sp.gr. 1.02), respectively. Calculate the mass
flux of A if its diffusivity is 2.5X10-9 m2/s.

7/29/2021 73
Assignment-3 Liquid-Liquid system

• 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 972.8
kg/m3. At point 2, the concentration of ethanol is
6.8 wt% and density is 988.1 kg/m3.The
diffusivity of ethanol is 0.740 × 10-9 m2/s.
Calculate the steady state flux NA.

7/29/2021 74
 Problem
At one point in the distillation column,the vapour
contains 70 mol% benzene and the adjacent liquid
reflux contains 59 mol% benzene. The temperature
at this point is 365 K. Assuming the diffusional
resistance to vapour transfer to be equivalent to the
diffusional resistance of a stagnant vapour layer 0.2
mm thick, calculate the rate of interchange of
benzene and toluene between vapour and liquid.
The molar latent heats of the two materials can be
taken as equal. The vapour pressure of toluene at
365 K is 54.0 kN/m2 and the diffusivity of the
vapours is 0.051 cm2/s.
7/29/2021 75
 THANK YOU

7/29/2021 76