Mass Transfer Operations I

by
Prof. Bishnupada Mandal
Professor and Head, Department of Chemical Engineering
IIT Guwahati, Guwahati 781039

Lecture 1

Introduction to Mass Transfer Operations

What are the Central Topics in Chemical Engineering?

1. Synthesis of Materials
2. Remediation of polluted air, water and soil
3. Energy Generation

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 constituents has been practiced for a long time. For
example

1. Extract metals from ores, perfumes from flower, and dyes from plants.
2. Evaporate sea water to obtain salt
3. Distil liquors.

The human body could not function for long, if it had no kidney- a membrane that selectively
removes water and waste products of metabolism from blood.

In chemical industries although chemical reactor is the central feature but separation cost
dominates the major part of the process cost.

The separation cost directly depends on the final to initial concentration of the separated
substances. If this ratio is larger, then the product cost is large. For example, sulphuric acid is
relatively low price product since sulphur is found naturally in a relatively pure state but pure uranium
is expensive due its low concentration found in nature.
 Chemical engineers are more concerned with the manufacture of chemicals using economical,
large-scale separation methods which are significantly different from laboratory techniques. For
example, chemist may separate hydrocarbon mixtures by gas- liquid chromatography but in a large
manufacturing plant, distillation is used to separate the same hydrocarbon mixture.

There are many separation methods which are based on entirely mechanical, for example,

i. Filtration of solids from a suspension in liquid.

ii. Obtain different particle size by screening.

WHAT IS MASS TRANSFER?

Mass transfer is the net movement of a component in mixture from one location to another where
the component exist at different concentration.

Flow of a liquid through a pipe and transport of solids through a conveyor belt are not mass
transfer operation

Common Examples
i. Lump of sugar added to a cup of tea: dissolves and diffuses throughout uniformly
ii. Deliberate use of Agarbati: Fragrance spreads uniformly throughout
iii. Drying of cloths under the SUN: Moistures diffuses into the air
Examples on Industrial Processes
i. Separation of CO2 from Flue Gas: Absorption
ii. Separation of a mixture of Ethanol and Water into its components: Distillation
iii. Separation of mixtures of Toluene and Water using Benzene as solvent: Extraction
iv. Drying of wet solid such as wood with the help of air: Drying

The chemical separation methods include absorption, distillation, liquid-liquid extraction, drying,
as well as newer methods such as adsorption and membrane separation.

Knowing the principle of separation operations, chemical engineers can successfully develop,
design and operate industrial processes.

Classifications of mass transfer operations

The three states, gas, liquid and solid can lead to six possibilities of phase contact.

1. Gas-Gas: Almost all gases are completely soluble in each other and practically this system is
not realized.
2. Gas-Liquid:
 Absorption: It is an operation in which a gas mixture is contacted with a liquid for the
purposes of preferentially dissolving one or more components of the gas and to provide a
solution of them in liquid.
Consider solute changing hands between gas & liquid
(Draw figure and show)
e.g.: If NH3- air mixture is brought in contact with water, a large portion of NH3 but
essentially no air dissolve in water.
Distillation: It is an equilibrium stage operation. In each stage, a vapour phase is contacted
with the liquid phase. Mass is transferred from vapour to liquid and from liquid to vapour.
The less volatile, heavy or high boiling component concentrate in the liquid phase and
more volatile, light components concentrate in the in the vapour. By using multiple stages in
series with recycle, separation can be accomplished.
e.g.: separation of petroleum crude into gasoline, kerosene, fuel oil & lubricating stock.
3. Gas-solid:
Drying: If a wet solid is exposed to a relative dry air the liquid leaves the solid and diffuses
into the gas.
Consider solute changing hands between solid & gas
(Draw figure and show)
e.g.: Drying of wood or laundry by exposure to air are the example.
Adsorption: If the diffusion takes place in the opposite direction, the operation is known as
adsorption.
Consider solute changing hands between gas & solid
(Draw figure and show)
e.g: If mixtures CH4, C2H6, C3H8 are brought into contact with a activated carbon, the hydro-
carbon are adsorbed in different extents, leads to a separation of gas mixture.
4. Liquid-liquid:
Extraction: Separation involving two immiscible liquid phases. Here a solution (called feed)
is brought into intimate contact with a second immiscible or slightly miscible liquid (called
solvent) in order to achieve transfer of solute from the feed to the solvent.
e.g.: separation of acetone from acetone-water mixture using carbon tetra chloride as a
solvent.
5. Liquid-solid:
Crystallization: Process of formation of solid from a liquid solution based on difference in
solute concentration and its solubility at a certain temperature.
e.g.: obtain sugar (an important component of our diet) from sugar cane or sugar beet; Sodium
chloride from sea water
 Leaching: Selective dissolution of a component from solid particles by a liquid solvent.
e.g.: leaching of medicinal compounds from plants.
Dissolutions of one or more substances from solid particles accompanied by chemical
reactions.
e.g.: leaching of gold from its ores by sodium cyanide solutions is the typical example.
6. Solid-Solid: the rate of diffusing in solid-solid system is very slow, so there is no such
industrial separation process.

Mechanisms of Mass Transfer

Mass transfer occurs by two basic mechanisms:

1. Molecular Mass Transfer: Molecular diffusion by random and spontaneous

microscopic movement of individual molecules in a gas, liquid or solid, as a result of thermal
motion and
2. Convective mass transfer: Eddy diffusion by random macroscopic fluid motion.

Driving Force for Mass Transfer

In a two-phase system not at equilibrium such as a layer of ammonia and air as a gaseous mixture
in contact with a layer of liquid water, spontaneous alteration through molecular diffusion occurs,
ultimately bringing the entire system to a state of equilibrium, whereupon alteration stops. At the
end, we observe that the concentration of any constituent is the same throughout a phase, but it
will not necessarily be the same in both phases. Thus the ammonia concentration will be uniform
throughout the liquid and ~ uniform at a different value throughout the gas. On the other hand, the
chemical potential of ammonia (or its activity if the same reference state is used), which is
differently dependent upon concentration in the two phases, will be uniform everywhere
throughout the system at equilibrium, and it is this uniformity which has brought the diffusive
process to a halt evidently, then, the true driving force for diffusion is activity or chemical
potential and not concentration. In multiphase systems, however, we customarily deal with
diffusional processes in each phase separately, and within one phase it is usually described in
terms of that which is most readily observed, namely, concentration changes.
Lecture 2

Molecular diffusion
Movement of individual molecules through a substance by virtue of their thermal energy
Explanation by simplified kinetic theory
A molecule is imagined to travel in a straight line at a uniform vel. until it collides with
another molecule, whereupon its vel. changes both in magnitude and direction.
Avg. distance the molecule travels bet. Collisions is its mean free path.
Molecule travels through a highly zigzag path, net distance travels in one direction in a given
time is the rate of diffusion.

Rate of Molecular Diffusion

Rate of Molecular Diffusion is very slow
increase with decreasing pr. (reduces no. of collisions), and
Increase with increasing temp. (Increases the molecular vel.)

Effect of Barrier on Molecular Diffusion

Rate of evaporation of water at 25C into a complete vacuum is roughly 3.3 kg/(s m2) of
water surface
Placing a layer of stagnant air at 1 std atm pr. and only 0.1mm thick above the water surface
reduces the rate by a factor of about 600

Molecular Diffusion vs. Eddy Diffusion

Consider a tank of 1.5m in dia and a salt solution to a depth of 0.75m is placed
A 0.75 m-deep layer of pure water carefully placed over the brine without disturbing the brine
Salt conc. at the top surface will be about 85% of its final value after 10 years and will reach
98 to 99% of its final value only after 28 years.
Impellor rotating in the tank at 22 r/min will bring about complete uniformity in about 60s
CONCENTRATIONS
Concentrations can be represented in different ways.
Mass Concentrations
Mass concentration of component i

=

Total mass concentration

=
=1

Mass fraction

= =



Sum of mass fraction


=

=1 =1

Molar Concentrations
Molar concentration of component i

=

Total molar concentration

=
=1

Total molar concentration for ideal gas mixtures

1
= =

=1
Mole fraction of component i (liquid or solid)

=

Mole fraction of component i (gases)

=

Mole fraction of component i (ideal gas mixture)

=

Sum of mole fractions
= 1; = 1
Example 1.1

The feed gas to an absorber has the following composition at 313 K and 200 kPa in the fig 1.

Calculate
i. Composition of the feed gas in terms of mass fractions.
ii. Total mass concentration of the feed gas.
Solution:
(i) Basis: 100 kmol of feed gas mixture

Table
Components kmol Molecular Wt. Mass (kg) Mass Fractions
CH4 90 16 1440.00 0.80
C2H6 5 30 150.00 0.08
nC3H8 4 44 176.00 0.09
nC4H10 1 58 58.00 0.03
100 1824.00 1.0

200
(ii) Total molar concentration (C) = = 8.314 313 = 0.077 3
1824.00
Average molecular weight( ) = = 18.24 kg/kmol
100

Total mass concentration () = = 0.077 ( 3
) 18.24 () = 1.40 3
Example 1.2

A liquid mixture contains 30wt% NaNO3 and 70wt% H2O. The solution temperature is 300K and the
density of the solution is assumed to be 1050 kg/m3.

Calculate

i. The composition in terms of mole fractions.

ii. The total molar concentrations.

Solution

Basis: 1 kg of liquid mixture

Component Mass (kg) Molecular wt. kmol Mole fractions

NaNO3 0.3 85 0.0035 0.08
H2O 0.7 18 0.0389 0.92
Total 1.0 0.0424 1.0

1 1
Average molecular weight ( ) = = 0.0424 = 23.585

1050 3
Total molar concentration () = = 23.585 = 44.52 3

DIFFUSION VELOCITIES
Mass Average Velocity
Defined in terms of mass concentrations

=1

Vmassavg = = =1 ( ) = =1
=1

= absolute velocity of species i with respect to a fixed reference frame

= mass fraction of species i

Molar Average Velocity

Defined in terms of molar concentrations

=1
Vmolavg =
= =1 ( ) = =1
=1

= mole fraction of species i

Example 1.3

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 0.05m/s,
0.03m/s, 0.02m/s and 0.03m/s, calculate the mass average and molar average velocities of the
mixture.

Solution

Rename H2:1, CO: 2, CO2:3 and N2: 4

The volume average velocity (= molar average velocity) given by
1
Vmolavg = (1 1 + 2 2 + 3 3 + 4 4 ) = 1 1 + 2 2 + 3 3 + 4 4 )

Here y1 is the mole fraction of component i in the gas mixture. Putting the values, we get

Vmolavg = (0.15)(0.05) + (0.3)(0.03) + (0.05)(0.02) + (0.5)(0.03) = 0.0325

The mass average velocity is given by

1
Vmassavg = (1 1 + 2 2 + 3 3 + 4 4 )


= =


= =

=
=
=
=
Now,
= 1 1 + 2 2 + 3 3 + 4 4
= (0.15)(2) + (0.3)(28) + (0.05)(44) + (0.5)(28) = 24.9
1
Vmassavg = =4
=1

1
Vmassavg = (1 1 1 + 2 2 2 + 3 3 3 + 4 4 4 )

(0.15)(2)(0.05)+(0.3)(28)(0.03)+(0.05)(44)(0.02)+(0.05)(28)(0.03)
Vmassavg = 24.9

Vmassavg = 0.014 /
FLUXES

Flux: Rate of transport of species i through unit area normal to the transport.

Flux of a given species is a vector quantity.

Flux may be calculated w.r.t coordinates fixed in space and coordinates moving with the mass or
molar average velocity.

Mass Flux

Calculated w.r.t coordinates fixed in space or Relative to stationary observer

: =

: =

Calculated w.r.t mass average velocity or Relative to an observer moving with the mass
average velocity

: = ( )

Molar Flux

Calculated w.r.t coordinates fixed in space or Relative to stationary observer

: =
, =

Calculated w.r.t molar average velocity or Relative to an observer moving with the
molar average velocity

: = ( )
Relation between Fluxes
= ( )
=

=

= +
Similarly,
= +
Questions and Answers
1. Under what conditions are the mass average velocity and molar average velocity of the
components of a mixture equal?
Answer: when the molecular weight of the components are same.
2. What is SI unit of molar flux?
Answer: kmol/m2s
3. Identify the correct answer to the following
Which of the following relations is correct for a gas mixture containing 40% CO2 and
60% C3H8 at 1 atm and 30C?
(i) Vmass avg > Vmolavg

(ii)Vmass avg = Vmolavg

(iii) Vmass avg < Vmolavg

Answer: (ii) Vmass avg = Vmolavg
4. Pick up correct statement
Molecular diffusion is caused by
i. Transfer of molecules from low concentration to high concentration region.
ii. Thermal energy of the molecules.
iii. Activation energy of the molecules.
iv. Potential energy of the molecules.
Answer: (ii) thermal energy of the molecule
Lecture 3 Fick's law (steady & unsteady)

Ficks law :

Ficks first law defines the diffusion flux of a component A in an isothermal, isoberic binary system is
proportional to the concentration gradient in a particular direction.
For diffusion of component A only in the x direction is

, =

, = molar flux of component A in the x direction.

= Concentration of A
= the diffusion coefficient or diffusivity of component A in B
on of species A and B

Q. Show that for a binary mixture A and B, the mutual diffusivities are same, i.e. =

Solution

We know that,

= + N (1)

For gas mixture

= (2)


= + = + (3)

Similarly,

= + (4)

Summing up the above two equations

+ = + + = +

( + ) (5)
Since for two component

+ = , + = 1 + = 0, so =


= + +1 (6)

Hence, = (proved)
Unsteady state diffusion

The change of concentration of a component of the diffusive constituents in a mixture over a time is
unsteady state of diffusion.

Balance Equation:
In + Generation = out + accumulation

Mass Flow rate of component A In

= [, | + , | + , | ] (1)

Where,

, = flux in the x direction

, | = value of flux at location x

= molecular weight of A

Generation of A by Chemical Reaction:

Let the rate of reaction = ( )

Rate of generation or production

= (2)
Mass rate of flow out An elemental Volume

= [, |+ + , |+ + , |+ ] (3)

Rate of Accumulation

= (4)

= density of A
,
In + Generation = out + accumulation

[, | + , | + , | ] + =

[, |+ + , |+ + , |+ ] + (5)

 [(, |+ , | ) + (, |+ , | ) + ( , |+


, | ) ] + = (6)

Now divided both side by 0, 0 0

We have

For Component A

, , ,
( + + )+ = (7a)

For Component B

, , ,
( + + )+ = (7b)

Total Material balance after adding (7a) and (7b)

( + ) ( + ) ( + ) ( + )
+ + +

= +

( + ) ( + ) ( + )
+ + + =0 (8)

Where = + = solution density

+ = 0,

&

, + ,
=
+
= , + ,
= , + ,
= , + ,

= , + ,

=
 , =

, =

( + )
= + (9)

(9) (8)

( +
+

) +

+

+

+

= 0 (10)

This is the equation of continuity or a mass balance for a total substance.

If the solution density is constant from equation (10)

+ + =0 (11)

We know that in terms of mass flux & in the x- direction.

, = +,

(12)

(13)

Eq. (7a) then becomes,

(14)

When = constant, using equation (11) and dividing in equation (14), we have
fick's law for unsteady state:

(15)

In the special case, where velocity equals to zero & there is no chemical reaction, from equation (15):

(16)

This is frequently applicable to diffusion in solids and to limited situation in fluid.

Lecture 4

STEADY STATE MOLECULAR DIFFUSION IN FLUIDS UNDER STAGNANT AND

LAMINAR FLOW CONDITIONS

Steady state diffusion through a constant area

Assume steady state diffusion in the x-direction without any chemical reaction in a binary
gaseous mixture of species A and B. For one dimensional diffusion of species A, the equation
of molar flux can be written as
dy A
N A CD A B yA N (1)
dx
Where N = N A + N B

Separating the variables in equation (1), it can be expressed as

dy A dx
(2)
N A y A N CD A B

For the gaseous mixture, at constant pressure and temperature C and D AB are constant,
independent of position and composition. Also all the molar fluxes are constant in equation
(2). Therefore the equation (2) can be integrated between two boundary conditions as
follows:
at x= x1, yA = yA1
at x = x2, yA = yA2
Where 1 indicates the start of the diffusion path and 2 indicates the end of the diffusion path.

Integrating eq (2) with the above BCs:

=

Let =
=

d =

Substituting the values in above equation

=


( ) = ( )


( ) = ( )

( ) = ( )

( )

[( ] = ( )
)

( )
= ( )
[
]
( )

( )
= ( )
[
]
( )

After integration with the above boundary conditions the equation for diffusion for the said
condition can be expressed as
NA
y A2
N A CD A B N
NA ln (3)
N x 2 x1 N A
y A1
N

Steady State Diffusion through Non-Diffusing B:

For steady state one dimensional diffusion of A through non-diffusing B, NB = 0 and NA =
constant. Therefore N A / N N A /( N A N B ) 1 . Hence equation (3) becomes

CD A B 1 y A2
NA ln (4)
x 2 x1 1 y A1

Pt p
Since for an ideal gas C and for mixture of ideal gases y A A , the equation (4) can
RT Pt
be expressed in terms of partial pressures as

D A B Pt Pt p A2
NA ln (5)
( x 2 x1 ) RT Pt p A1

where Pt is the total pressure and pA1 and pA2 are the partial pressures of A at point 1 and 2
respectively. For diffusion under turbulent conditions, the flux is usually calculated based on
linear driving force. For this purpose the equation (5) can be manipulated to rewrite it in
terms of a linear driving force. Since for the binary gas mixture of total pressure Pt,
Pt = pA + pB

Pt p A2 p B2 ; Pt p A1 p B1 ; p A1 p A2 pB2 pB1

Then the equation (5) can be written as

DA B Pt p A1 p A2 pB2
NA ln (6a)
RT ( x2 x1 ) pB2 pB1 pB1

Or

p
DA B Pt
NA p A2 (6b)
RT ( x2 x1 ) pBLM
A1

Where p B , M is called logarithmic mean partial pressure of species B which is defined as

p B2 p B1
p BLM (7)
pB
ln 2
pB
1
dy A
The component A diffuses by concentration gradient . Here flux is inversely
dx
proportional to the distance through which diffusion occurs and the concentration of the
stagnant gas ( p BLM ) because with increase in x and p BLM , resistance increases and flux
decreases.

Example 1:
CO2 is diffusing through non diffusing air under steady state conditions at a total pressure of
1 atmosphere and temperature 300K. The partial pressure of CO2 is 20kPa at one point and
5kPa at other point. The distance between the points is 5cm. Calculate the flux of CO2. Given
that = 2 x 10-5 m2/s at 300K and 1 atm.

Solution:
Assume ideal gas
Let air = B

= ( , )
( ) ,
Given
=
P = 1 atm = 101.3 kPa = 1.013 Pa
T= 300 K, = = .
, = = ,

, = = ,

=
,1 = 2,1 = (101.3 20) = 81.3

, = , = (. ) = .
, , . .
= = = . =
.
(, ) (. )
,

1.013 105
2 = (20,000 5,000) Pa
300 K 0.05 88590

2 105 1.013 105 15000

=
8314 300 0.05 88590 2

= 2.75 106 2

Steady state equimolar counter diffusion:

This is the case for the diffusion of two ideal gases, where an equal number of moles of the
gases diffusing counter-current to each other. In this case NB = -NA = constant and NA+NB =
0. The molar flux equation (equation (1) at steady state can then be written as

= +


=

=

D AB Pt dy A
NA (8)
RT dx
Integrating the equation (8) with the boundary conditions: at x = x1, yA = yA1; at x = x2
yA = yA2, the equation of molar diffusion for steady-state equimolar counter diffusion can be
represented as
DAB Pt
NA ( y A1 y A2 )
RT ( x2 x1 )
(9)
DAB
( p A1 p A2 )
RT ( x2 x1 )
Example 2

CO2 is diffusing at steady state through a straight tube of 0.5m long with an inside diameter of 0.05m
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 2 2 = 4 105 2 / at 300K and 1atm. Calculate the

following for steady state equimolar counter diffusion:

a. Molar flow rate of CO2

b. Molar flow rate of N2

Solution:

Assume ideal gas in equimolar counter diffusion for CO2 flux:

2 2
2 = ( 2 ,2 )
(2 1 ) 2 ,1

Given

=
= 1 atm = 101.3 kPa = 1.013 Pa
T= 300 K, = .
, = = ,

, = = ,

22
a) 2 = (2 1 )
(2 ,1 2 ,2 )

4 105
= (15,000 5,000)
8314 300 0.5

0.4
= = 3.21 107 2
1247100

Now, molar flow rate of CO2 = NCO2 x A

Where A= cross sectional area of the tube

Given that internal diameter of the tube (Di) = 0.05 m

 2
= = (0.05)2 = 1.96 103 2
4 4

CO2 = 3.21 107 2
1.96 103 2 = 6.29 1010

22
b) 2 = (2 ,1 2 ,2 )
(2 1 )

, = , = (. ) = . = 86300 Pa

, = , = (. ) = . = 96300 Pa

DCO2-N2 = DN2-CO2

4 105 0.4
= (86300 96300) = = 3.21 107 2
8314 300 0.5 1247100

N2 = 3.21 107 1.96 103 2
2

= 6.29 1010

Non-equimolar counter diffusion solve problem

In many situations, A and B molecules diffuse in opposite directions at different molar velocities. Let
us consider the following reaction. 2A+B = 2C

When one mole B diffuses towards A and two moles of A diffuse in opposite direction. Here,
N A N B / 2 . Hence,
Lecture 5 Variable cross section Area

Diffusion through variable cross-sectional area

Steady state diffusion through a stagnant gas film

Figure 1: Schematic of diffusion of A through a uniformly tapered geometry

Consider a component A is diffusing at steady state through a equilateral triangle conduit which is
tapered uniformly as shown in Figure 1. At point 1 the side of the triangle is a1 and at point 2 it is a2.
At position x in the conduit, A is diffusing through stagnant, non-diffusing B.

For an equilateral triangle, the formula for area (where = length of one side) is:

1
=
2

3
altitude ( ) for equilateral triangle
2

1 3 3 2
= =
2 2 4

Returning to the Fick's Law formula, at position x the flux of A through a triangle of stagnant B can
be written as

4
(1 )= , = =
3 2

= /
Where

4
=
32
Before limits are imposed, it must be remembered that is a function of x, as the size of triangle
uniformly tapers with distance along the duct:

2 1
= 1 + ( 1 )
2 1

2 1 2 1
= 1 +
2 1 2 1 1

2 1 2 1 2 1
=0+ (1) (0) =
2 1 2 1 2 1

2 1
=
2 1

We can now substitute x for a in the expression, and integrate with limits of pA1 at triangle of side a1
and pA2 when the triangle is of side a2:

2 1 2 4 2

=
2 1 1 32 1

x2 x1 1 a2
4RT pA
=> [a] = [ln(Pt pA )]pA2
3DAB a2 a1 a1 1

x2 x1
4RT 1 1 Pt pA
(a a ) = ln (P p 2 )
3DAB a2 a1 1 2 t A1

Pt pA
(a1 a2 ) =

3DAB Pt a2 a1
(x ) ln (P p 2 )
a a 1 2 4RT 2 x1 t A1

3DAB Pt a1 a2 Pt pA2
=
ln ( )
4RT x2 x1 Pt pA1
Example Problem 1:

The CO2 is diffusing through non-diffusing N2 at steady state in a conduit of 2m long at 300K and a
total pressure of 1 atmosphere. The partial pressure of CO2 at the left end is 20kPa and 5kPa at the
other end. The cross section of the conduit is in the shape of an equilateral triangle being 0.0.025m at
the left end and tapering uniformly to 0.05m at the right end. Calculate the rate of transport of CO2.
The diffusivity is DAB = 210-5 m2/s.

Solution:

Given that

m2
DAB = 2 105
s
R = 8314 (m3.Pa)/(kmol K)

T = 300K

Pt = 1 atm = 101.3 kPa = 1.013 105 Pa

PA1 = 20kPa = 20 103 Pa

PA2 = 5kPa = 5 103 Pa

1 = 0.025

2 =0.05 m

x2 x1 = 2 m
Now substituting values in the following equation

3DAB Pt a1 a2 Pt pA2

NA = ln ( )
4RT x2 x1 Pt pA1

m2
3 2 105 s 101.3 103 Pa 0.025m 0.05 101.3 103 Pa 5 103 Pa
= ln ( )
(m3 . Pa) 101.3 103 Pa 20 103 Pa
4 8314 300K 2m
kmol. K

3 2 105 101.3 103 0.025 0.05 101.3 103 5 103

= ln ( )
4 8314 300 2 101.3 103 20 103

0.22 102 96.3 103

= ln ( )
9976800 81.3 103

= 3.74 1011 kmol/s

 Diffusion from a sphere

There are lots of examples where diffusion can take place through the spherical shape bodies. Some
examples are:

Evaporation of a drop of liquid

The evaporation of a ball of naphthalene
The diffusion of nutrients to a sphere-like microorganism in a liquid
Assume a constant number of moles NA of A from a sphere (area = 4r2) through stagnant B as shown
in Figure.

Figure 1.5: Schematic of diffusion from a sphere

From the Ficks law of diffusion, the rate of diffusion can be expressed as:

(1)
P -D dP NA
N A 1- A = AB A where N A =
Ptotal RT dr 4r 2
-RTN A dr dPA
Ptotal
-DAB dPA 4DAB r N A Ptotal PA
2 (2)
= where NA =
RT dr 4r 2
PA -DAB dPA NA
dr dPAN A 1- P = RT dr where N A = 4r 2
Ptotal total
2
Ptotal PA (3)
-RTN A dr dPA
Ptotal
4DAB r 2
Ptotal PA

A 1 with limits of PA2 at r2 and P

2r
Integrating
-RTN P A1 at r1 gives:
Ptotal ln(Ptotal PA ) PA2
4DAB r r1 A1

(4)
-RTN A 1 1 Ptotal PA2
ln
4DAB Ptotal r1 r2 Ptotal PA1
 As A r2, then 1/r
r1 <<
RTN 2
Ptotal 0: pA2 pA1 pA2
ln
4r1DAB Ptotal P
total pA1 PBM
(5)
N A DAB Ptotal (pA1 pA2 )
N A1 , the flux at the surface
4r12 RTPBLM r1

This equation can be simplified if PA1 is small compared to P (a dilute gas phase), PBM P. Also
setting 2r1 = D1, diameter, CA1 = PA1/RT

DAB
N A1 = (CA1 - CA2 ) (6)
D1

Example Problem 2

A sphere of naphthalene having a radius of 5 mm is suspended in a large volume of still air at 310 K
and 1 atm. The partial pressure at the surface of naphthalene at 310K is 50 Pa. Assume dilute gas
phase. The DAB of naphthalene in air at 310 K is 610-6 m2/s. Calculate the rate of evaporation of
naphthalene from the surface.

Solution:

DAB = 610-6 m2/s

PA1 = 50 Pa
PA2 = 0,
r1 = (5/1000) m,
R = 8314 (m3.Pa)/ (kmol K)
RTN A Ptotal PA2 PA1 PA2
PBLM = Pt =
1 ln
atm = 1.013 105 Pa
= 101.3kPa
4r1DAB Ptotal Ptotal PA1 PBM
N A DAB Ptotal (PA1 PA2 )
N A1 , the flux at the surface
4r12 RTPBM r1

After substitution,

5
6106 1.013 10 50
= 5
8314 310 1.013 10 0.005

303.9106
= 13054.22
= 0.023 106 kmol/ m2 . s
Steady state equimolar counter diffusion:

Figure 3: Schematic of diffusion of A through a uniformly tapered tube

Consider a component A is diffusing at steady state through a circular conduit which is tapered
uniformly as shown in Figure 3. At point 1 the radius is r1 and at point 2 it is r2.

We know that

dyA
NA = C DAB + yA N
dx

DAB dyA
= P + yA N
RT t dx

At position x in the conduit, A is diffusing through B by equimolar counter diffusion.

Now for equimolar counter diffusion. NA = NB , N = NA + NB = 0

At position x the flux can be written as

pA
DAB d ( Pt ) DAB dpA
NA = P =
RT t dx RT dx

A DAB dpA
N
NA = =
r 2 RT dx

Using the geometry as shown, the variable radius r can be related to position x in the path as follows:

r2 r1
Again, r = ( ) x + r1
x2 x1
A x2
N dx DAB pA2
2 = dpA
x1 r r RT pA
[(x2 x1 ) x + r1 ] 1
2 1

r2 r1
Let, C1 = ( )
x2 x1

A x2
N dx DAB pA2
= dpA
x1 [C1 x + r1 ]2 RT pA
1

Let C1 x + r1 = z

dz
dx =
C1

Now substituting in above equation

dz
A z2 C1
N DAB pA2
= dpA
z1 [z]2 RT pA
1

NA 1 z2 DAB
=> [ ] = [pA ]ppA2
C1 z z1 RT A1

NA 1 1 DAB
=> [ ]= [p pA2 ]
C1 z1 z2 RT A1

NA 1 1 DAB
=> [ ]= [p pA2 ]
C1 C1 x1 + r1 C1 x2 + r1 RT A1

A
N 1 1 DAB
r2 r1 [ r r r r ]= [pA1 pA2 ]
( ) ( 2 1 )x1 + r1 ( 2 1 )x2 + r1 RT
x2 x1 x2 x1 x2 x1

r r
DAB ( 2 1 ) [pA 1 pA2 ]
A =
N
x2 x1
RT
1 1
[ r r r r ]
( 2 1 )x2 + r1 ( 2 1 )x1+ r1
x2 x1 x2 x1

If x1 =0 and x2=L i.e. x2-x1 = L

r r
( 2 1 ) [pA 1 pA2 ]
A = DAB
N L
1 1
DAB
= RT
r1 r2
(pA1 pA2 )
RT [ ] L
r2 r1
Example Problem 3:

The CO2 is diffusing at steady state through N2 by equimolar counter diffusion in a conduit 2 m long
at 300K and a total pressure of 1 atmosphere. The partial pressure of CO2 at the left end is 20 kPa and
5 kPa at the other end. The cross section of the conduit is in the shape of cylindrical of radius is
0.025m at the left end and tapering uniformly to a radius of 0.05m at the right end. Calculate the
molar flow rate of CO2. The diffusivity is DAB = 210-5 m2/s.

Solution:

Given that

Given that

m2
DAB = 2 105
s
R = 8314 (m3.Pa)/(kmol K)

T = 300K

Pt = 1 atm = 101.3 kPa = 1.013 105 Pa

PA1 = 20kPa = 20 103 Pa

PA2 = 5kPa = 5 103 Pa

1 = 0.025

2 =0.05 m

L = x2 x1 = 2 m
Now substituting values in the following equation

DAB r1 r2

NA = (pA1 pA2 )
RT L

m2
2 105 s 3.14 0.025m 0.05
= (20 103 5 103 )
(m3. Pa)
8314 300K 2m
kmol. K

0.0078515
= 102
4988400

= 2.36 1010 kmol/s

Lecture 6 Diffusion Co-efficient measurement & prediction

DIFFUSION COEFFICIENT: MEASUREMENT AND PREDICTION

The proportionality factor of Ficks law is called diffusivity or diffusion coefficient which
can be defined as the ratio of the flux to its concentration gradient and its unit is m 2/s. It is a
function of the temperature, pressure, nature and concentration of other constituents.
Diffusivity of gases decreases with increase in pressure ( DAB 1 / p for moderate ranges of

pressures, up to 25 atm) because number of collisions between species is less at lower

pressure. But the diffusivity is hardly dependent on pressure in case of liquid. The diffusivity
increases with increase in temperature ( DAB T 1.5 ) because random thermal movement of

molecules increases with increase in temperature. The diffusivity is generally higher for gases
(in the range of 0.5105 to 1.0 10-5 m2/s) than for liquids (in the range of 1010 to 10-9
m2/s). The diffusivity value of the gases into solids is in the range of 10 13 to 10-10 m2/s. The
diffusivity of permanent gases is in the order of 10-10 m2/s for polymer.

Measurement of gas-phase diffusion coefficient

There are several methods of experimental determination of gas-phase diffusion coefficient. Two
methods are (a) Twin-bulb method and (b) Stefan tube method. Predictive equations are sometimes
used to determine diffusivity. These may be empirical, theoretical or semi-empirical.

(a) Twin-bulb method

Two large bulbs are connected by a narrow/capillary tube. The schematic representation is shown in
Figure 6.1. There is a suitable arrangement for stirring the contents of the bulbs to maintain the
uniform concentrations in the bulbs. In the beginning two bulbs are evacuated and all the three valves
[Va1, Va2 and VaT] are kept closed. Then Va1 is opened and bulb 1 is filled with pure A at a total
pressure Pt. After that Va2 is opened and bulb 2 is filled with pure B at the same pressure Pt. The valve
VaT is opened and diffusion proceeds for some period of time (say t) and then the valve is closed. The
samples from the individual chambers are collected and analyzed their composition.

Assumptions:

(i) Negligible capillary volume

(ii) Each bulb is always of a uniform concentration

(iii) Pseudo-steady state diffusion through the capillary

(Pseudo-steady state approximation: This means that, at any instant, diffusion through the connecting
tube occurs at steady state. As the concentration in the bulbs change a little, a new steady state of
diffusion is attained simultaneously. This assumption is correct if the time scale for the change of
concentration in the bulbs is considerably larger than the time scale for attainment of steady state of
diffusion through the connecting tube.)

Fig. 6.1: A schematic of the twin bulb apparatus

Consider, Ax is the inner cross sectional area, L is the length of connecting capillary tube, v1 and v2
are the volumes, and pA1 and pA2 (pA1 > pA2) are the partial pressures of component A at any time t, in
the bulbs 1 and 2, respectively. Because the total pressures in the bulbs remain constant and equal,
equimolar counter diffusion will occur.

At steady state the transport of A from bulb 1 to bulb 2 can be written as follows.

A x D AB (p A1 p A 2 )
Ax NA A x N B (6.1)
RTL

If pA1 and pA2 are partial pressures of A in two bulbs at any time, for ideal gases:

v1 dp A1
Ax NA (6.2)
RT dt

v 2 dp A 2
and Ax NA (6.3)
RT dt

(pA1 decreases with time while pA2 increases with time and hence there is negative sign in equation
(6.2))

From equations (6.2) and (6.3) we have

 d(p A1 p A 2 ) 1 1
A x N A RT (6.4)
dt v1 v 2

d(p A1 p A 2 ) A x D AB (p A1 p A 2 ) 1 1
(6.5)
dt L v1 v 2

Using the following conditions:

t =0; (pA1-pA2) = (Pt-0) = Pt

t=t, (pA1-pA2) = p A1, t p A 2, t

Applying the above boundary conditions, Equation (6.5) is integrated to obtain the expression of DAB
as follows:

Pt A D 1 1
ln x AB t derive this relation (6.6)
(p A1,t p A 2,t ) L v1 v 2

The parameters to be measured from the experiment:

(i) Initial pressure in the vessels

(ii) Partial pressures of one of the components in the vessel at the end of the experiment

(iii) Time of experiment to be recorded

Mutual diffusion coefficient is then can be calculated directly from equation (6.6)
Example problem 6.1:

To measure the diffusivity of CO2 by two-bulb method, the pure CO2 and pure N2 is filled in bulb 1
and bulb 2, respectively. The volume of bulb 1 is 4 liters and bulb 2 is 3 liters. These two bulbs are
connected by a capillary tube of 5 cm length and 2 cm internal diameter. The partial pressures of CO2
in the bulbs 1 and 2 are 60 kPa and 40 kPa, respectively at the end of 6 hours. The bulbs are
maintained at 100kPa total pressure and 313K temperature. Calculate the diffusivity of CO2.

Solution:

We know that

Pt A D 1 1
ln x AB t
(p A1,t p A 2,t ) L v1 v 2

Or

Lv 1 v 2 Pt
D AB ln
A x t v 2 v1 (p A1, t p A 2, t )

Given:

L = 5 cm = 0.05 m

v1 = 4 lit = 0.004 m3

v2 = 8 lit = 0.003 m3

Ax = d2/4 = (210-2 m)2/4 =3.1410-4 m2

Pt = 100kPa

pA1 = 60kPa

pA2 = 40kPa

t = 6 hours = 360 60 seconds = 21600 seconds

0.05m 0.004 m 3 0.003 m 3 100kPa

D AB

3.14 10 m 21600 s 0.003 m 0.004 m
-4 2 3 3
ln

(60kPa 40kPa )

= 2 10-5 m2/s
(b) Stefan tube method

Stefan tube consists of a vertical narrow glass tube joined to a horizontal larger diameter tube to form
a tee (T). The vertical tube is held at a constant temperature water bath. Component B (say Air) is
pumped through the horizontal tube. Volatile component (A) is taken in the narrow vertical tube.
Evaporated A diffuses through B and reaches to the top of the vertical tube and then swept away by
the flowing B. Component B is assumed to be insoluble in A and hence considered to be non-
diffusing B. The liquid level in the vertical tube will drop very slowly and pseudo-steady state
condition can be assumed. This means that as soon as there is a small drop in level, a new steady state
rate of diffusion is established simultaneously.

Fig. 6.2: A representation of the Stefan tube

Let, at any time t, partial pressure of A at the h distance from the top of the vertical tube is pA1 and
that at the top it is pA2. The diffusional flux of A through non-diffusing B can be written as:

D AB Pt (p A1 p A 2 )
NA (6.7)
RT h p BLM

Where

pB2 pB1 pA1 pA2

pBLM = p =
ln (pB2 ) P p
ln (Pt pA2 )
B1 t A1
Assuming a cross sectional area of 1 m2, the level drops dh meter in dt sec, and A(dh.1)/MA is the
kmol of A that has been left and diffused. Then

Flux Area = kmol A transferred/ time

A (dh.1)
NA . 1 = (6.8)
MA .dt

Boundary conditions:

(i) at t = 0, h = h0 and (ii) at t = tF, h = hF

Substituting the Equation (6.8) in Equation (6.7) and integrating with above BCs, one gets

A hF DAB Pt (pA1 pA2 ) tF

hdh
MA h0
= RT pBLM
0 dt (6.9)

(h2F h20 ) RT pBLM

t F = 2MA (6.10)
A DAB Pt (pA1 pA2 )

or

RT p BLM (h 2F h 02 )
D AB (6.11)
2Pt M A (p A1 p A 2 ) t F

Where, partial pressure of a at liquid surface, pA1 is equal to vapour pressure at the same temperature.
The partial pressure of A at the top of the vertical tube, pA2 is zero due to high flow rate of B.
Example problem 6.2:

To measure the diffusivity of water vapour by Stefan tube method, the water is filled in the vertical
narrow glass tube and held at a constant temperature of 30oC. The air is flowing through the
horizontal tube at a total pressure of 1 atmosphere and the temperature is 30 oC. Initially, the water
level was at distance of 1 cm from the top of the vertical tube and after 30 minutes the level drops to
1.2 cm from top. The vapour pressure of water at 30oC is 4.5kPa. Calculate the diffusivity of water
vapor.

Solution:

We know that

RT p BLM (h 2F h 02 )
D AB
2Pt M A (p A1 p A 2 ) t F

Given

R = 8314 (m3.Pa)/(kmol K)

T = 30oC = 273+ 30 = 303K

Pt = 101.3x 103 Pa

pA1 = 4.5 kPa = 4.5 x 103 Pa

pA2 = 0

MA = 18

ho = 1cm = 0.01m

hf = 1.2cm = 0.012m

tf = 30 min = 30 x 60 = 1800s

1 = 1 = (101.3 4.5) 103 = 96.8 103

2 = 2 = (101.3 0) 103 = 101.3 103

2 1 4.5 x 103
= 2 = = 105
( ) 101.3
( 96.8 )
1

8314 303 105 [(0.012)2 (0.01)2 ]

, =
2 101.3 103 18 1800 4.5 103

2519142 105 0.00004

= = 3.4 105 2 /
2953908 107
Lecture 7

Gas Phase Diffusion Coefficient Prediction, Liquid Phase Diffusion

Coefficient Measurement and Prediction

Predictive Equations:

Experimental diffusivities values for different binary gas mixtures are available in the literature. Still
there are several mixtures for which experimental data are not reported. In this situation, we can use
suitable correlation to predict the value of diffusivity.

(A) Empirical: Fuller, Schettler and Giddings Gas phase

A very simple and reasonably accurate empirical equation was suggested by Fuller, Schettler and
Giddings (1966) for the prediction of binary gas-phase diffusivity up to moderate pressures:

1
10 7 T 1.75 1 1 2 2
D AB 2
m /s
Pt A B 3
1
3
1 M A M B

where,

T is temperature in K

MA, MB are molecular weights of A and B

Pt is total pressure in atmosphere

A, B are atomic diffusion volume in m3.

Example 7.1

For mixtures of carbon monoxide and hydrogen, predict the diffusivity using the Fuller et al. (1966)
formulae for the following conditions:

(i) at 1 atmosphere pressure and 100oC temperature

(ii) at 2 atmosphere pressure and 100oC temperature

(iii) at 1 atmosphere pressure and 200oC temperature

Solution to Example Problem 7.1

Using Fuller et al.:

1 1
107 1.75 +

(i) D AB = 2
[( )13 +( )13 ]

Using atomic values from text book,

A= CO, B= H2

VA = 1(C) + 1(O) = 1(16.5) + 1(5.48) = 21.98

MA = 2(H) = 1(12) + 1(16) = 28 kg/kmol

VB = 2(2.31) = 4.62

MB = 2(1) = 2 kg/kmol

Temperature T = 100+273=373K

Formula is for pressure in ATMOSPHERES, so Pt=1 atm.abs

1 1
107 (373)1.75 + 31658.51 107 (0.732)
28 2
D AB = 2 = 1(19.98)
= 1.159 104 m2/s=1.16 104 m2/s
1[(21.98)13 +(4.62)13 ]

A only 3 significant figures are available in the question, 1.159 104 m2/s

(ii) There is no need to calculate the other diffusivities from scratch, as they all have the same
molecular volumes and weights, i.e. at same temperature

1
D AB

DAB2 1
=
1 2

1
DAB2 = ( ) 1
2

So now the new diffusivities can be calculated by adjusting the first one for pressure. It is best to
use the accurate value and approximate later.

2 = 2 , 1 = 1.159 104 m2/s

 1 m2
2 = ( ) 1.159 104 = 0.5795 104 2
2 s

i.e as only 3 significant figures are available in the question , 0.5795 104 2

(iii) There is no need to calculate the other diffusivities from scratch, as they all have the same
molecular volumes and weights, i.e. at same pressure

D AB 1.75

DAB2 2 1.75
=( )
1 1

2 1.75
DAB2 = ( ) 1
1

1 = 100 + 273 = 373, 2 = 200 + 273 = 473. 1 = 1.159 104 2

473 1.75 m2
DAB2 =( ) 1.159 104 = 1.761 104 m2 s
373 s

i.e as only 3 significant figures are available in the question , 1.761 104 2

(A) Theoretical: Chapman-Enskog equation

There is a useful correlation suggested by Chapman and Enskog. This correlation is based on the
kinetic theory of gases and the diffusion coefficient is strongly dependent on the binary
interaction parameter of mixture pair.

1
1.858 10 7 T 1.5 1 1 2
D AB
Pt AB D
2
MA MB

Where, T is temperature in K

MA, MB are molecular weights of A and B

Pt is total pressure in atmosphere

( A B )
AB is characteristic length parameter of binary mixture in
2

D is collision integral = f(kT/AB)

The following equations can be used to calculate AB

AB = ( A B)0.5

Example 7.2

For mixtures of ammonia and hydrogen, predict the diffusivity using the Chapman-Enskog formulae
at 1 atmosphere pressure and 100oC temperature

Solution:

MA = NH3 = 17; MB = H2 = 2

T = 100oC =100+ 273= 373 K

Pt = 1 atmosphere

The Lennard-Jones parameters are:

NH3: A = 2.900Ao; A/k = 558.3

H2: B = 2.827Ao; B/k = 59.7

( A B ) (2.900 2.827) o
NH3 (A) H2 (B) pair: AB 2.8635 A
2 2

AB A B
1/ 2

558.3 59.7 182.6

1/ 2

k k k

kT 373
2.04
AB 182.6

From the collision integral

D = 1.075

1
1.858 10 7 T 1.5 1 1 2
D AB
Pt 2AB D MA MB

1
1.858 107 (373)1.5 1 1 2
= [ + ] = 1.134 104 2 /
1 (2.8635)2 1.075 17 2
Measurement of liquid-phase diffusion coefficient

There are few methods of determination of liquid-phase diffusivities. The most commonly used
method is Diaphragm cell method.

(A) Diaphragm Cell Method

Diaphragm cell contains two compartments as shown in the Fig 7.1. These are separated by
diaphragm.

Figure 7.1: diaphragm cell

In this measurement a very dilute solution in one compartment and a solution of slightly higher
concentration in other compartment are placed. Molecular diffusion takes place through the narrow
pores of the diaphragm cell.

Let the area of the diaphragm is A and porosity is .

Effective area for diffusion = A

The lengh of diffusion path is not equal to the thickness of the diaphragm since the pores are not
straight. To account for this a tortuosity factor must be introduce.

average or effective length of diffusive path

= diaphragm thickness (xd )
(7.1)

where is tortuosity. As the solute concentration is very low, bulk flow term can be taken as zero.
Hence,
 equimolar counter type
dC A (C C A 2 ) (C C A 2 )
N A D AB D AB A1 D AB A1 (7.2)
dh (h 2 h 1 ) x

where (h 2 h1 ) = xd

We can write the flux equations for both sides of the diaphragm

dC A1
v1 AN A (7.3)
dt

dC A 2
and v 2 AN A (7.4)
dt

Adding Equations (7.3) and (7.4) and substituting NA from Equation (7.2) we have,

d(C A1 C A 2 ) AD AB (C A1 C A 2 ) 1 1
(7.5)
dt xd v1 v 2

If CA1,0 and CA2,0 are the initial concentrations

Boundary conditions

t=0, CA1=CA1,0; CA2=CA2,0

t=tF, CA1=CA1,F; CA2=CA2,F

1
x 1 1 C A1, 0 C A 2, 0 C C A 2, 0
Therefore, D AB d ln 1 ln A1, 0 (7.6)
AtF
v1 v 2 C A1,F C A 2,F t F C A1,F C A 2,F

A 1 1
where
x d v1 v 2

is the cell constant and can be determined by using a solute of known diffusion coefficient.

Example 7.3 To measure the diffusivity of acetone in water at 20oC a diaphragm cell is used.
Initially, compartment 1 of volume 50 cm3 is filled with 0.5 molar acetone in water and the
compartment 2 of volume 55 cm3 is filled with water. The molar concentration of acetone dropped to
0.4 molar in compartment 1 after 40 hours. The cell constant is given as 0.3cm-2. Calculate the
diffusivity of acetone.
Solution:
Given:
v1 = 50 cm3; v2 = 55 cm3
tf = 40 hours = 406060 seconds = 144000 seconds
= 0.3cm-2

at t =0, CA1,0 = 0.5 and CA2,0 = 0

At t =tf, CA1,F = 0.4 and CA2,F = ?

Material Balance on acetone

v1 CA1,0 + v2 CA2,0 CA2,0= v1 CA1,F + v2 CA2,F

500.5 + 550 = 500.4 +55 CA2,F

CA2,F = 0.091

Now,

1 C A1,0 C A 2,0 1 0.5 0 2

D AB ln
ln cm / s
t F C A1,F C A 2,F 0.3 144000 0.4 0.091
1.11 10 5 cm2 / s 1.11 10 9 m 2 / s

(B) Semi-empirical equation: Wilke-Chang Equation

1.173 10 16 (M B ) 0.5 T 2
D AB m /s (7.7)
B 0A.6

where, D AB is diffusivity of solute A in solvent B, m2/s, is association factor [for H2O=2.26;

MeOH=1.9; EtOH=1.5; non-associated solvent=1.0]; MB is molecular weight of B; T is absolute
temperature in K; B is solution viscosity, kg/m.s; A is solute molar volume at normal boiling point,
m3/kmol [A=0.0756 m3/kmol for H2O as solvent].

Example 7.4 Predict the diffusivity of acetone in water at 20oC using Wilke-Chang equation. The
association factor for water is 2.26. The molar volume of acetone is 0.074 m3/kmol. The viscosity of
water at 20oC is 1.00210-3 kg/m s.

Solution:

1.173 10 16 (M B ) 0.5 T 1.173 10 16 (2.26 18) 0.5 293

D AB 1.04 10 9 m2/s
B 0A.6 1.002 10 3 (0.074) 0.6
(C) Stokes-Einstein Equation

The Stokes-Einstein equation, one of the first theories, was derived for a very large spherical molecule
(A) diffusing in a liquid solvent (B) of small molecules. Stokes law was used to determine the drag
on the moving solute molecule. Then the equation was modified by assuming that the all molecules
are alike and arrange in a cubic lattice and expressing the molecular radius in terms of molecular
volume:

9.96 10 16 T
D AB
v1A/ 3 (7.8)

where, D AB is diffusivity of solute A in solvent B, m2/s; T is absolute temperature in K; is viscosity

of solution, kg/m.s; A is solute molar volume at normal boiling point, m3/kmol. This equation applies
very well to a very large unhydrated and sphere-like solute molecules of about 1000 molecular weight
or greater or where the vA is above about 0.5 m3/kmol in aqueous solution.

Liquid diffusivity varies linearly with absolute temperature and inversely proportional to viscosity of
the medium. The well known Stokes-Einstein equation shows this type of dependency as given below:

D AB
Cons tan t (7.9)
T