Molecular Diffusion

Dr. P. A. Joshi
Professor, Dept .of Chem. Engg.
Faculty of Technology
Dharmsinh Desai University, Nadiad
[email protected]
 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

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 Diffusion in liquid state

: Ink dye

: Water
molecules

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 Diffusion in liquid state

: Ink dye

: Water
molecules

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 Diffusion in gaseous state

: Perfume
molecules
: Air
molecules
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 Diffusion in gaseous state

: Perfume
molecules
: Air
molecules
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 Net Movement
Note: This barrier does
not illustrate a
partially permeable
membrane.

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 Net Movement

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 Equilibrium
When particles reaches an equilibrium, does
the particles stop moving?

Particles move in a random and dynamic

motion.
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 Concentration Gradient
The concentration difference between regions of high
concentration and low concentration.
High concentration
gradient

Down the
concentration
gradient

Low
concentration
gradient

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 Concentration Gradient
Which slide will allow you to go down faster?

Obviously-A
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 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

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 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
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 Molecular Diffusion
• 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.

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 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 positio
in space which is important for designing MT equipment and J
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  D m

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
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Diffusion in binary solutions-Relation Between NA & JA

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 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

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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)

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 Molecular Diffusion in Gases

Eq. 2.22 becomes

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 Relation Between NA and NB

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 Situations Encountered
• Steady State
• Unsteady state
• Diffusion In Gases
• Diffusion in Liquids
• Unimolecular Diffusion
• Equimolar Diffusion

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

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Steady State Diffusion of A through Non-
diffusing B, i.e, NA=Const, NB=0

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 Steady State Diffusion of A through Non-
diffusing B

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 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
dc A
N A, z
  D AB  y A N A, z  N B , z 
dz
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 • In equimolar counterdiffusion, NA,z = -NB,z
dc A
N A , z   D AB
dz at z = z , c =
Integrated at z = z1, cA = cA1 and 2 A
cA2 to:

D
N  AB
(cA  cA )
 z1 )
A, z
( z2
1 2

• Or in terms of partial pressure,

D
N  AB
( pA  pA )
 z1 )
A, z
RT ( z 2 1 2

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 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

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 Steady-State Equimolar Counter
Diffusion

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 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,

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 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.

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 a) Steady State Unimolecular Diffusion

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 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. Dr P A Joshi, DDU, Nadiad
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 Diffusivity of Gases
Wilke-Lee modification of Herschfelder-Bird-Spotz
For nonpolar gases or a polar and nonpolar gas

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 Diffusivity in Gases:
Pressure dependence of diffusivity is given by
(for moderate ranges of
pressures, upto 25 atm).
• And temperature dependency is according
to

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 Diffusivity in Liquids
Wilke-Chang equation for estimation of liquid diffusivity

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 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 m / sec. 2

• Liquids : 10 –6 ------------- 10 -9 m / sec.

2

• Solids : 5 X 10 –1 4 ------------- 1 X 10 -1 0 m / sec.

2

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 Equation of Continuity- Fick’s Second Law

---(2.18)

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 Flow past a solid surface

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

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 Momentum & Heat Transfer

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

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
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A Joshi, Actual values are near by
DDU, Nadiad 41
 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

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 Mass, Momentum & Heat Transfer

Under simplified conditions, the mass, momentum and heat trans

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

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 Illustration

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 Example
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.
 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.

NA=

NA= (6.1-11)
• Also, from the perfect gas law, pAV=nART, and

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

NA= (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,NAusing
= SI units,
• If pressures in atm are used with SI unit,

NA=

• Other driving forces (besides concentration

differences) for diffusion also occur because of
temperature, pressure, electrical potential, and
other gradients.
 Example
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
 Solution
• Equation (2.34) can be used, where P = 1.0132 x 105 Pa, z2 -z1 = 0.10 m,
and T = 298 K. Substituting into Eq. (2.34) for part (a),

• Rewriting Eq. (2.34) for component B for part (b) and noting that pB1 = P
– pA 1 = 1.01325 x 105 – 1.013 x 104 = 9.119 x 104 Pa and pB2 = P – pA 2
= 1.01325 x 105 – 0.507 x 104 = 9.625 x 104 Pa.

• The negative for J*B means the flux goes from point 2 to point 1.
 Example
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.
 Solution
• The diffusivity is converted to ft2/h by using the conversion
factor:

• From Appendix A.2 the vapor pressure of water at 20 °C is 17.54

mm, or pA1 = 17.54/760 = 0.0231 atm = 0.0231(1.01325 x 105) =
2.341 x 103 Pa, pA2 = 0 (pure air). Since the temperature is 20 °C
(68 °F), T = 460 + 68 °R = 293 K. From Appendix A.1, R = 0.730
ft3.atm/lb mol.°R . To calculate the value of pBM
• Since pB1 is close to pB2, the linear mean (pB1+pB2)/2
could be used and would be very close to pBM.
• Substituting into Eq. (2.30) with z2-z1 = 0.5 ft
(0.1524m),
 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

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 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.

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 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.
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 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.
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 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.
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 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

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 Evaporation of Benzene in Air

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 Solution

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 XBM

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 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.

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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]

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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.

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 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.
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 THANK YOU

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