PRINCIPLES OF MASS TRANSFER

INTRODUCTION
Mass Transfer When a component in a mixture migrates in the same phase or from
phase to phase because of a difference in concentration
Examples of mass transfer
Evaporation of water in the open pail to the atmosphere
Coffee dissolves in water
Oxygen dissolves in the solution to the microorganism in the fermentation
process
Reaction occurs when reactants diffuse from the surrounding medium to the
catalyst surface
Possible driving force for mass transfer
Concentration difference
Pressure difference
Electrical gradient, etc
TYPES OF MASS TRANSFER

Types of Mass Transfer

1. Molecular diffusion
Transfer of individual molecules through a fluid by random movement From
high concentration to low concentration
E.g. a drop of blue liquid dye is added to a cup of water the dye molecules
will diffuse slowly by molecular diffusion to all parts of the water.
To increase this rate of mixing of the dye, the liquid can be mechanically
agitated by a spoon and convective mass transfer will occur.
2. Convective mass transfer
Using mechanical force or action to increase the rate of molecular diffusion
E,g stirred the water to dissolve coffee during coffee making
FDE 312- PART1: MOLECULAR DIFFUSION-1

PART I- MOLECULAR MASS TRANSPORT

1.1 Introduction to mass transfer
1.2 Properties of mixtures
1.2.1 Concentration of species
1.2.2 Mass Averaged velocity
1.3 Diffusion flux
1.3.1 Ficks Law
1.3.2 Relation among molar fluxes
1.4 Diffusivity
1.4.1 Diffusivity in gases
1.4.2 Diffusivity in liquids
1.4.3 Diffusivity in solids
1.5 Steady state diffusion
1.5.1 Diffusion through a stagnant gas film
1.5.2 Pseudo steady state diffusion through a stagnant gas film.
1.5.3 Equimolar counter diffusion.
1.5.4 Diffusion into an infinite stagnant medium.
1.5.5 Diffusion in liquids
1.5.6 Mass diffusion with homogeneous chemical reaction.
1.5.7 Diffusion in solids
1.6 Transient Diffusion.

1.1 Introduction to Mass Transfer

When a system contains two or more components whose concentrations vary from
point to point, there is a natural tendency for mass to be transferred, minimizing the
concentration differences within a system. The transport of one constituent from a
region of higher concentration to that of a lower concentration is called mass
transfer.
The transfer of mass within a fluid mixture or across a phase boundary is a process
that plays a major role in many industrial processes. Examples of such processes are:
(i)
(ii)
(iii)
(iv)
(v)

Dispersion of gases from stacks

Removal of pollutants from plant discharge streams by absorption
Stripping of gases from waste water
Neutron diffusion within nuclear reactors
Air conditioning

FDE 312- PART1: MOLECULAR DIFFUSION-2

Many of day-by-day experiences also involve mass transfer, for example:

(i)

A lump of sugar added to a cup of coffee eventually dissolves and then

eventually diffuses to make the concentration uniform.
Water evaporates from ponds to increase the humidity of passing-airstream
Perfumes present a pleasant fragrance which is imparted throughout the
surrounding atmosphere.

(ii)
(iii)

The mechanism of mass transfer involves both molecular diffusion and convection.
1.2 Properties of Mixtures
Mass transfer always involves mixtures. Consequently, we must account for the
variation of physical properties which normally exist in a given system. The
conventional engineering approach to problems of multicomponent system is to
attempt to reduce them to representative binary (i.e., two components) systems.
In order to understand the future discussions, let us first consider definitions and
relations which are often used to explain the role of components within a mixture.
1.2.1 Concentration of Species:
Concentration of species in multicomponent mixture can be expressed in many ways.
For species A, mass concentration denoted by A is defined as the mass of A, m A per
unit volume of the mixture.

A =

mA
V

------------------------------------ (1)

The total mass concentration density is the sum of the total mass of the mixture in
unit volume:

where i is the concentration of species i in the mixture.

Molar concentration of, A, C A is defined as the number of moles of A present per unit
volume of the mixture.
By definition,
FDE 312- PART1: MOLECULAR DIFFUSION-3

Number of moles =

mA
MA

mass of A
molecular weight of A

----------------------------- (2)

Therefore from (1) & (2)

C

nA
A
=
V
M A

For ideal gas mixtures,

n

PA V

nA
P
= A
V
RT

[ from Ideal gas law PV = nRT]

RT

where P A is the partial pressure of species A in the mixture. V is the volume of gas, T
is the absolute temperature, and R is the universal gas constant.
The total molar concentration or molar density of the mixture is given by
C =

1.2.2 Velocities
In a multicomponent system the various species will normally move at different
velocities; and evaluation of velocity of mixture requires the averaging of the
velocities of each species present.
If i is the velocity of species i with respect to stationary fixed coordinates, then
mass-average velocity for a multicomponent mixture defined in terms of mass
concentration is,

FDE 312- PART1: MOLECULAR DIFFUSION-4

By similar way, molar-average velocity of the mixture * is

*=

For most engineering problems, there will be title difference in * and and so the
mass average velocity, , will be used in all further discussions.
The velocity of a particular species relative to the mass-average or molar average
velocity is termed as diffusion velocity
(i.e.) Diffusion velocity = i -
The mole fraction for liquid and solid mixture, x A ,and for gaseous mixtures, y A , are
the molar concentration of species A divided by the molar density of the mixtures.
xA =

CA
C

CA
C

(liquids and solids)

(gases).

The sum of the mole fractions, by definition must equal 1;

(i.e.)

=1

=1

by similar way, mass fraction of A in mixture is;

wA =

FDE 312- PART1: MOLECULAR DIFFUSION-5

Example 1.1
O2
CO
CO 2
N2

The molar composition of a gas mixture at 273 K and 1.5 x 10 5 Pa is:

7%
10%
15%
68%

Determine
a)
b)
c)
d)

the composition in weight percent

average molecular weight of the gas mixture
density of gas mixture
partial pressure of O 2 .

Calculations:
Let the gas mixture constitutes 1 mole. Then
O2
CO
CO 2
N2

= 0.07 mol
= 0.10 mol
= 0.15 mol
= 0.68 mol

Molecular weight of the constituents is:

O2
CO
CO 2
N2

= 2 x 16 = 32 g/mol
= 12 + 16 = 28 g/mol
= 12 + 2 x 16 = 44 g/mol
= 2 x 14 = 28 g/mol

Weight of the constituents is: (1 mol of gas mixture)

O2
CO
CO 2
N2

= 0.07 x 32 = 2.24 g
= 0.10 x 28 = 2.80 g
= 0.15 x 44 = 6.60 g
= 0.68 x 28 = 19.04 g

Total weight of gas mixture = 2.24 + 2.80 + 6.60 + 19.04

= 30.68 g
Composition in weight percent:
2.24
O2 =
x100 = 7.30%
30.68
FDE 312- PART1: MOLECULAR DIFFUSION-6

2.80
x100 = 9.13%
30.68
6.60
CO 2 =
x100 = 21.51%
30.68
19.04
N2 =
x100 = 62.06%
30.68

CO =

Weight of gas mixture

Number of moles
30.68
M=
= 30.68 g mol
1

Average molecular weight of the gas mixture M =

Assuming that the gas obeys ideal gas law,

PV = nRT
n
P
=
V RT
n
= molar density = m or C
V
Therefore, density (or mass density) = m M
Where M is the molecular weight of the gas.

PM (1.5 x10 5 ) x30.68

Density = m M =
=
kg m 3
RT
8314 x 273
= 2.03 kg/m 3
Partial pressure of O 2 = [mole fraction of O 2 ] x Total pressure
=

7
x 1.5 x10 5
100

= 0.07 ( 1.5 x 10 5)
= 0.105 x 10 5 Pa

FDE 312- PART1: MOLECULAR DIFFUSION-7

1.3 Diffusion flux

Just as momentum and energy (heat) transfers have two mechanisms for transportmolecular and convective, so does mass transfer. However, there are convective
fluxes in mass transfer, even on a molecular level. The reason for this is that in mass
transfer, whenever there is a driving force, there is always a net movement of the
mass of a particular species which results in a bulk motion of molecules. Of course,
there can also be convective mass transport due to macroscopic fluid motion. In this
chapter the focus is on molecular mass transfer.
The mass (or molar) flux of a given species is a vector quantity denoting the amount
of the particular species, in either mass or molar units, that passes per given
increment of time through a unit area normal to the vector. The flux of species
defined with reference to fixed spatial coordinates, N A is
N

= C A

---------------------

(1)

This could be written in terms of diffusion velocity of A, (i.e.,

velocity of mixture, , as
N

=C

= * =

By definition

) + C A

- ) and average

---------- (2)

Therefore, equation (2) becomes

N

= C A (
=C

) +

CA
C

) + y

For systems containing two components A and B,

N
N

) + y A (C A A + C B B )

= C A (

) + y A (N

= C A (

) + y

=C

+ N B)

------------------------------- (3)

The first term on the right hand side of this equation is diffusional molar flux of A,
and the second term is flux due to bulk motion.

FDE 312- PART1: MOLECULAR DIFFUSION-8

1.3.1 Ficks law:

An empirical relation for the diffusional molar flux, first postulated by Fick and,
accordingly, often referred to as Ficks first law, defines the diffusion of component A
in an isothermal, isobaric system. For diffusion in only the Z direction, the Ficks rate
equation is
JA = D

AB

dC A
dZ

where D AB is diffusivity or diffusion coefficient for component A diffusing through

component B, and dC A / dZ is the concentration gradient in the Z-direction.
A more general flux relation which is not restricted to isothermal, isobasic system
could be written as
J A = C DA B

dyA
dZ

----------------- (4)

using this expression, Equation (3) could be written as

N

= C DA B

dyA
+ y AN
dZ

--------------- (5)

1.3.2 Relation among molar fluxes:

For a binary system containing A and B, from Equation (5),
N A= J

or

=N

A
A

+ y AN
y AN

----------------------- (6)

Similarly,
=N

yBN

-------------------- (7)

Addition of Equation (6) & (7) gives,

J

+J

= N A + N B ( y A + y B) N

---------- (8)

By definition N = N A + N B and y A + y B = 1.
Therefore equation (8) becomes,
FDE 312- PART1: MOLECULAR DIFFUSION-9

JA+JB=0
J A = -J B
C D AB
From

dyA
dyB
= C D BA
dz
dZ

--------------- (9)

yA+yB=1
dy A = - dy B

Therefore Equation (9) becomes,

D AB = D BA ----------------------------------- (10)
This leads to the conclusion that diffusivity of A in B is equal to diffusivity of B in A.
1.4 Diffusivity
Ficks law proportionality, D AB , is known as mass diffusivity (simply as diffusivity) or
as the diffusion coefficient. D AB has the dimension of L 2 / t, identical to the
fundamental dimensions of the other transport properties: Kinematic viscosity, =
( / ) in momentum transfer, and thermal diffusivity, (= k / C ) in heat transfer.
Diffusivity is normally reported in cm2 / s; the SI unit being m2 / s.
Diffusivity depends on pressure, temperature, and composition of the system.
In table, some values of D AB are given for a few gas, liquid, and solid systems.
Diffusivities of gases at low density are almost composition independent, incease
with the temperature and vary inversely with pressure. Liquid and solid diffusivities
are strongly concentration dependent and increase with temperature.
Table 1.1 : General range of values of diffusivity:
Gases :
Liquids :
Solids :

5 x 10 6
10 6
5 x 10 14

-------------------------------------

1 x 10-5
10-9
1 x 10-10

m2 / s
m2 / s
m2 / s

In the absence of experimental data, semi theoretical expressions have been

developed which give approximation, sometimes as valid as experimental values, due
to the difficulties encountered in experimental measurements.
FDE 312- PART1: MOLECULAR DIFFUSION-10

1.4.1 Diffusivity in Gases:

Pressure dependence of diffusivity is given by
1
(for moderate ranges of pressures, up to 25 atm)
P
and temperature dependency is according to
D

AB

D AB T

Diffusivity of a component in a mixture of components can be calculated using the

diffusivities for the various binary pairs involved in the mixture. The relation given by
Wilke is
D 1 mixture =

1
y 3

y
y 2
+
+ ........... + n
D1 2
D13
D1 n

where
D 1-mixture is the diffusivity for component 1 in the gas mixture
D 1-n is the diffusivity for the binary pair, component 1 diffusing through component n
y n is the mole fraction of component n in the gas mixture evaluated on a
component 1 free basis, that is

y2 =

y2
y2 + y3 + ....... yn

Example 1.2. Determine the diffusivity of CO 2 (1), O 2 (2) and N 2 (3) in a gas mixture
having the composition:
CO 2 : 28.5 %
O 2 : 15%
N 2 : 56.5%
The gas mixture is at 273 K and 1.2 x 10 5 Pa. The binary diffusivity values are given as:
(at 273 K)
D 12 P = 1.874 m 2 Pa/s
D 13 P = 1.945 m 2 Pa/s
D 23 P = 1.834 m 2 Pa/s

FDE 312- PART1: MOLECULAR DIFFUSION-11

Calculations:
Diffusivity of CO 2 in mixture
D 1m =

y2

D 12

1
+

where y 2 =

y3
D 13
y2
y2 + y3

y3 =

y3
y2 + y3

Therefore D1m P =

0.15
= 0.21
0.15 + 0.565

0.565
= 0.79
0.15 + 0.565

1
0.21 0.79
+
1.874 1.945

= 1.93 m 2.Pa/s
Since P = 1.2 x 10 5 Pa,
1.93
= 1.61x10 5 m 2 s
5
1.2 x10

D 1m =

Diffusivity of O 2 in the mixture,

D 2m =

y1

D 21

1
+

Where y 1 =

y3
D 23
y1
y1 + y 3

0.285
= 0.335
0.285 + 0.565

(mole fraction on-2 free bans).

and

y3 =

and

y3
y1 + y 3

0.565
= 0.665
0.285 + 0.565

D 21 P = D 12 P = 1.874 m 2.Pa/s

FDE 312- PART1: MOLECULAR DIFFUSION-12

Therefore

D 2m =

D 2m P =

1
0.335 0.665
+
1.874 1.834

= 1.847 m 2.Pa/s

1.847
= 1.539 x10 5 m 2 sec
5
1.2 x10

By similar calculations diffusivity of N 2 in the mixture can be calculated, and is found

to be, D 3m = 1.588 x 10 5 m 2/s.
1.4.2 Diffusivity in liquids:
Diffusivity in liquid are exemplified by the values given in Table 1.1. Most of these
values are nearer to 10-5 cm2 / s, and about ten thousand times lower than those in
dilute gases. This characteristic of liquid diffusion often limits the overall rate of
processes accruing in liquids (such as reaction between two components in liquids).
In chemistry, diffusivity limits the rate of acid-base reactions; in the chemical industry,
diffusion is responsible for the rates of liquid-liquid extraction. Diffusion in liquids is
important because it is slow.
Certain molecules diffuse as molecules, while others which are designated as
electrolytes ionize in solutions and diffuse as ions. For example, sodium chloride
(NaCl), diffuses in water as ions Na + and Cl-. Though each ion has a different mobility,
the electrical neutrality of the solution indicates the ions must diffuse at the same
rate; accordingly it is possible to speak of a diffusion coefficient for molecular
electrolytes such as NaCl. However, if several ions are present, the diffusion rates of
the individual cations and anions must be considered, and molecular diffusion
coefficients have no meaning.
Diffusivity varies inversely with viscosity when the ratio of solute to solvent ratio
exceeds five. In extremely high viscosity materials, diffusion becomes independent
of viscosity.
1.4.3 Diffusivity in solids:
Typical values for diffusivity in solids are shown in table. One outstanding
characteristic of these values is their small size, usually thousands of time less than
those in a liquid, which are in turn 10,000 times less than those in a gas.
Diffusion plays a major role in catalysis and is important to the chemical/ food
engineer. For metallurgists, diffusion of atoms within the solids is of more
importance.
FDE 312- PART1: MOLECULAR DIFFUSION-13

1.5 Steady State Diffusion

In this section, steady-state molecular mass transfer through simple systems in which
the concentration and molar flux are functions of a single space coordinate will be
considered.
In a binary system, containing A and B, this molar flux in the direction of z, as given by
Eqn (5) is
dyA
N A = C D AB
+ y A ( N A + N B ) --- (1)
dz

1.5.1 Diffusion through a stagnant gas film

The diffusivity or diffusion coefficient for a gas can be measured, experimentally
using Arnold diffusion cell as shown in Fig 1.1.

Fig 1.1 Arnold diffusion cell

The narrow tube of uniform cross section which is partially filled with pure liquid A, is
maintained at a constant temperature and pressure. Gas B which flows across the
open end of the tub, has a negligible solubility in liquid A, and is also chemically inert
to A. (i.e. no reaction between A & B).
Component A vaporizes and diffuses into the gas phase; the rate of vaporization may
be physically measured and may also be mathematically expressed in terms of the
molar flux.

FDE 312- PART1: MOLECULAR DIFFUSION-14

Consider the control volume S z, where S is the cross sectional area of the tube.
Mass balance on A over this control volume for a steady-state operation yields
[Moles of A leaving at z + z] [Moles of A entering at z] = 0.
(i.e.)

SN

A z + z

SN

A z

= 0.

-------------- (1)

Dividing through by the volume, SZ, and evaluating in the limit as Z approaches
zero, we obtain the differential equation
dN A
= 0 ------------------------- (2)
dz
This relation stipulates a constant molar flux of A throughout the gas phase from Z 1
to Z 2 .
A similar differential equation could also be written for component B as,
dNB
= 0,
dZ
and accordingly, the molar flux of B is also constant over the entire diffusion path
from z 1 and z 2 .
Considering only at plane z 1 , and since the gas B is insoluble is liquid A, we realize that
N B , the net flux of B, is zero throughout the diffusion path; accordingly B is a
stagnant gas.
From equation (1) (of section 1.5)

FDE 312- PART1: MOLECULAR DIFFUSION-15

N A = C D AB

dyA
+ y A ( N A + N B)
dz

N A = C D AB

dyA
+ y AN
dz

Since N B = 0,

Rearranging,
NA =

C D AB d y A
1 y A d z

------------ (3)

This equation may be integrated between the two boundary conditions:

at z = z 1
Y A = Y A1
And
at z = z 2
Y A = y A2
Assuming the diffusivity is to be independent of concentration, and realizing that N A
is constant along the diffusion path, by integrating equation (3) we obtain
Z2

d z = C DAB

Z1

NA =

yA2

y A1

C D AB
Z2Z1

d y A
1 y A

1 y A2
ln
--------------(4)
1 y A1

The log mean average concentration of component B is defined as

y B , lm =

y B 2 y B1
y

ln B 2

y
B1

Since y B =1 y A ,

y B , lm =

(1 y

) (1 y
y

ln A 2
y A1

A2

A1

A1

y
ln

y
A2

A2

y A1

------- (5)

Substituting from Eqn (5) in Eqn (4),

FDE 312- PART1: MOLECULAR DIFFUSION-16

C D AB ( y A1 y
Z 2 z1
y B , lm

For an ideal gas C =

A2

-------------------- (6)

n
p
, and
=
V
RT

for mixture of ideal gases y

PA
P

Therefore, for an ideal gas mixture equation. (6) becomes

( p A1 p
D AB
RT ( z 2 z1 )
p B , lm

A2

This is the equation of molar flux for steady state diffusion of one gas through a
second stagnant gas.
Many mass-transfer operations involve the diffusion of one gas component through
another non-diffusing component; absorption and humidification are typical
operations defined by these equation.

Example 1.3 Oxygen is diffusing in a mixture of oxygen-nitrogen at 1 atm, 25C.

Concentration of oxygen at planes 2 mm apart are 10 and 20 volume % respectively.
Nitrogen is non-diffusing.
(a) Derive the appropriate expression to calculate the flux oxygen. Define units
of each term clearly.
(b) Calculate the flux of oxygen.
Diffusivity of oxygen in nitrogen = 1.89 x 10 5 m 2/s.
Solution:
Let us denote oxygen as A and nitrogen as B. Flux of A (i.e.) N A is made up of two
components, namely that resulting from the bulk motion of A (i.e.), Nx A and that
resulting from molecular diffusion J A :
N A = Nx A + J A ---------------------------------- (1)

FDE 312- PART1: MOLECULAR DIFFUSION-17

From Ficks law of diffusion,

dCA

J A = D AB

----------------------------------------- (2)

dz

Substituting this equation (1)

dCA

N A = Nx A D AB

--------------------------------- (3)

dz

Since N = N A + N B and x A = C A / C equation (3) becomes

N A = (N A + N B )

CA
C

D AB

dCA
dz

Rearranging the terms and integrating between the planes between 1 and 2,
dz

cD

AB

C A2

C A1

dC A

N AC C A (N A + N B )

-------------- (4)

Since B is non diffusing N B = 0. Also, the total concentration C remains constant.

Therefore, equation (4) becomes
C A2
dC A
z
=
C A1 N C N C
CD AB
A
A A

C C A2
1
ln
NA
C C A1

Therefore,
NA =

CD AB
z

ln

C C A2
C C A1

---------------------------- (5)

Replacing concentration in terms of pressures using Ideal gas law, equation (5)
becomes
NA =

D AB Pt
RTz

ln

Pt PA 2
Pt PA1

--------------------------- (6)

where
FDE 312- PART1: MOLECULAR DIFFUSION-18

D AB = molecular diffusivity of A in B
P T = total pressure of system
R = universal gas constant
T = temperature of system in absolute scale
z = distance between two planes across the direction of diffusion
P A1 = partial pressure of A at plane 1, and
P A2 = partial pressure of A at plane 2
Given:

D AB = 1.89 x 10 5 m2/s
P t = 1 atm = 1.01325 x 10 5 N/m 2
T = 25C = 273 + 25 = 298 K
z = 2 mm = 0.002 m
P A1 = 0.2 x 1 = 0.2 atm (From Ideal gas law and additive pressure rule)
P A2 = 0.1 x 1 = 0.1 atm

Substituting these in equation (6)

NA =

(1.89 x10 )(1.01325x10 ) ln 1 0.1

5

(8314)(298)(0.002)

1 0.2

= 4.55 x10 5 kmol/m 2.s

1.5.2 Pseudo steady state diffusion through a stagnant film:
In many mass transfer operations, one of the boundaries may move with time. If the
length of the diffusion path changes a small amount over a long period of time, a
pseudo steady state diffusion model may be used. When this condition exists, the
equation of steady state diffusion through stagnant gas can be used to find the flux.
If the difference in the level of liquid A over the time interval considered is only a
small fraction of the total diffusion path, and t 0 t is relatively long period of time, at
any given instant in that period, the molar flux in the gas phase may be evaluated by

C D AB ( y

A1

zy B , lm

A2

------------------ (1)

where z equals z 2 z 1 , the length of the diffusion path at time t.

The molar flux N A is related to the amount of A leaving the liquid by

FDE 312- PART1: MOLECULAR DIFFUSION-19

A, L

where

MA

A, L d z

-------------------------- (2)

MA dt

is the molar density of A in the liquid phase

under Psuedo steady state conditions, equations (1) & (2) can be equated to give

A, L

C D AB ( y A1 y
dz
=
dt
z y B , lm

A2

--------------- (3)

Equation. (3) may be integrated from t = 0 to t and from z = z t0 to z = z t as:

A,L y B , lm M

dt = C D

t =0

AB

(y

A1

Zt

z dz

A2

Zt 0

yielding

t=

A,L y B , lm M

z t2 z t20

C D AB ( y A1 y A 2 )
2

-------- (4)

This shall be rearranged to evaluate diffusivity D AB as,

D AB =

A,L y B , lm

z t2 z t20

M A C ( y A1 y A 2 ) t
2

Example 1.4 A vertical glass tube 3 mm in diameter is filled with liquid toluene to a
depth of 20mm from the top opened. After 275 hrs at 39.4 C and a total pressure of
760 mm Hg the level has dropped to 80 mm from the top. Calculate the value of
diffusivity.
Data:

vapor pressure of toluene at 39.4C = 7.64 kN / m2,

density of liquid toluene = 850 kg/m3
Molecular weight of toluene = 92
(C 6 H 6 CH 3 )

D AB

A, L y Blm

Z t2 Z

=
M A C ( y A1 y A 2 )t
2

2
t0

FDE 312- PART1: MOLECULAR DIFFUSION-20

y B 2 y B1

where y B , l m =

y
ln B 2
y B1

y B2 = 1 y A2
y A1 =

p A1
P

y B1 = 1 y A1

7.64
101.3

(760 mm Hg = 101.3 kN/m2)

= 0.0754

y B1 = 1 0.0754 = 0.9246
y A2 = 0
y B = 1 y A2 = 1
Therefore y B , lm =

C=

1 0.9246
= 0.9618
1
ln

0.9246

P
1.01325 x10 5
= 0.039 k mol /m3
=
R T 8314 x(273 + 39.4 )

D AB =

Therefore

0.08 2 0.02 2
850 x0.9618

92 x0.039 x(0.0754 0 )x 275 x3600

2

= 1.5262 x 10 3 (0.08 2 0.02 2)

= 9.1572 x 10-6 m2/s
1.5.3 Equimolar counter diffusion:
A physical situation which is encountered in the distillation of two constituents
whose molar latent heats of vaporization are essentially equal, stipulates that the
flux of one gaseous component is equal to but acting in the opposite direction from
the other gaseous component; that is, N A = - N B .
The molar flux N A , for a binary system at constant temperature and pressure is
described by

or

dyA
+ y A ( N A + N B)
dz
dC A
+ y A ( N A + N B)
dz

= C D AB

= D AB

------- (1)

with the substitution of N B = - N A , Equation (1) becomes,

FDE 312- PART1: MOLECULAR DIFFUSION-21

= D AB

dC A
dz

----------------- (2)

For steady state diffusion Equation. (2) may be integrated, using the boundary
conditions:
at z = z 1
C A = C A1
and z = z 2
C A = C A2
Giving,
Z2

dz

NA

= D AB

Z1

CA 2

dC

C A1

from which

D AB
(C
z 2z1

A1

A2

------------------- (3)

nA
p
= A .
V
RT
Therefore Equation. (3) becomes

For ideal gases, C

D AB
( P A1 P A 2 ) ---------- (4)
R T ( z 2 z 1)

This is the equation of molar flux for steady-state equimolar counter diffusion.
Concentration profile in these equimolar counter diffusion may be obtained from,
d
( N A) = 0 (Since N A is constant over the diffusion path).
dz

And from equation. (2)

N

= D AB

d CA
.
dz

Therefore

FDE 312- PART1: MOLECULAR DIFFUSION-22

d
dz

d CA
= 0.
D AB
d z

d 2 CA
= 0.
dz2

or

This equation may be solved using the boundary conditions to give

C A C

A1

C A1 C

A2

zz1
z1 z 2

-------------- (5)

Equation, (5) indicates a linear concentration profile for equimolar counter diffusion.
Example 1.5. Methane diffuses at steady state through a tube containing helium. At
point 1 the partial pressure of methane is p A1 = 55 kPa and at point 2, 0.03 m apart P
A2 = 15 kPa. The total pressure is 101.32 kPa, and the temperature is 298 K. At this
pressure and temperature, the value of diffusivity is 6.75 x 10 5 m 2/s.
i)
ii)

calculate the flux of CH 4 at steady state for equimolar counter

diffusion.
Calculate the partial pressure at a point 0.02 m apart from point 1.

Calculation:
For steady state equimolar counter diffusion, molar flux is given by
NA =

D AB
RT z

(p

A1

p A 2 ) --------------------------- (1)

Therefore;
NA =

6.75 x 10 5
(55 15) kmol
8.314 x 298 x0.03
m 2 . sec

= 3.633 x10 5

kmol
m 2 sec

And from (1), partial pressure at 0.02 m from point 1 is:

3.633 x10 5 =

6.75 x10 5
(55 p A )
8.314 x 298 x0.02

p A = 28.33 kPa

FDE 312- PART1: MOLECULAR DIFFUSION-23

Example 1.6. In a gas mixture of hydrogen and oxygen, steady state equimolar
counter diffusion is occurring at a total pressure of 100 kPa and temperature of 20C.
If the partial pressures of oxygen at two planes 0.01 m apart, and perpendicular to
the direction of diffusion are 15 kPa and 5 kPa, respectively and the mass diffusion
flux of oxygen in the mixture is 1.6 x 10 5 kmol/m 2.s, calculate the molecular
diffusivity for the system.
Solution:
For equimolar counter current diffusion:
NA =

D AB
RTz

(p

A1

p A 2 ) ------------------------ (1)

where
N A = molar flux of A (1.6 x 10 5 kmol/m 2.s):
D AB = molecular diffusivity of A in B
R = Universal gas constant (8.314 kJ/kmol.k)
T = Temperature in absolute scale (273 + 20 = 293 K)
z = distance between two measurement planes 1 and 2 (0.01 m)
P A1 = partial pressure of A at plane 1 (15 kPa); and
P A2 = partial pressure of A at plane 2 (5 kPa)
Substituting these in equation (1)
1.6 x10 5 =

D AB

(8.314)(293)(0.01)

(15 5)

Therefore, D AB = 3.898 * 10 5 m 2/s

Example 3.7. A tube 1 cm in inside diameter that is 20 cm long is filled with CO 2 and
H 2 at a total pressure of 2 atm at 0C. The diffusion coefficient of the CO 2 H 2
system under these conditions is 0.275 cm2/s. If the partial pressure of CO 2 is 1.5 atm
at one end of the tube and 0.5 atm at the other end, find the rate of diffusion for:
i)
ii)
iii)

steady state equimolar counter diffusion (N A = - N B )

steady state counter diffusion where N B = -0.75 N A , and
steady state diffusion of CO 2 through stagnant H 2 (N B = 0)

FDE 312- PART1: MOLECULAR DIFFUSION-24

+ y A (N A + N B )

d yA

i) N A = C D AB

dz

Given
NB =-NA
Therefore N A = C D AB

d yA

= D AB

dz

dCA
dz

pA
RT
where p A is the partial pressure of A; such that p A + p B = P)

(For ideal gas mixture C A =

d ( p A RT )
dz
For isothermal system, T is constant
Therefore N A = D A B

Therefore N A =

D AB d p A

Z2

(i.e.)

N A d z =
Z1

NA =

RT

D AB
RT z

(p

A1

D AB
RT

dz
PA 2

d p

P A1

p A 2 ) ---------------------------------- (1)

where Z = Z 2 Z 1
Given: D AB = 0.275 cm 2/s = 0.275 x 10 4 m 2 /s ; T = 0C = 273 K
0.275 x 10 4
1.5 x1.01325 x10 5 0.5 x1.01325 x10 5
8314 x 273 x 0.2
k mol
= 6.138 x10 6 2
m sec
NA =

Rate of diffusion = N A S
Where S is surface area
Therefore rate of diffusion = 6.138 x 10-6 ( r 2 )
= 6.138 x 10 6 (0.5 x 10 2) 2
= 4.821 x 10 10 k mol/s
FDE 312- PART1: MOLECULAR DIFFUSION-25

= 1.735 x 10 3 mol/hr.
+ y A (N A + N B )
dz
given: N B = - 0.75 N A

ii) N A = C D AB

d yA

Therefore N A = C D AB

d yA

= C D AB

d yA

dz

dz

+ y A (N A 0.75 N

+ 0.25 y A N A

N A 0.25 y A N A = C D AB
N A d z = C D AB

d yA
dz

d yA
1 0.25 y A

for constant N A and C

Z2

y A2

Z1

y A1

N A d z = CD AB

d yA
1 0.25 y A

dx
1
a + b x = b ln (a + b x )

1
y
N A z = ( C D AB )
ln (1 0.25 y A ) y AA12
0
.
25

4 CD AB 1 0.25 y A 2
---------------------------------- (2)
ln
NA=
1 0.25 y 1
z
A

Given:
p
2 x1.01325 x10 5
=
= 0.0893 k mol m 3
RT
8314 x 273
p
1.5
y A1 = A1 =
= 0.75
P
2
p
0.5
y A2 = A2 =
= 0.25
P
2
Substituting these in equation (2),
C=

NA =

4 x0.0893(0.275 x10 4 )
0.2

1 0.25 x0.25
ln 1 0.25 x0.75

FDE 312- PART1: MOLECULAR DIFFUSION-26

kmol
m 2 sec
Rate of diffusion = N A S = 7.028 x10 6 (0.5 x 10 2) 2
= 5.52 x 10 10 kmol/s
= 1.987 x 10 3 mol/hr.
= 7.028 x10 6

iii) N A = CD AB

d yA
dz

+ y A (N A + N B )

Given: N B = 0
Therefore N A = CD AB
y A2

Z2

NA

d z = CD

Z1

AB

d yA
dz

d yA

1 y

y A1

+ yA NA

1 y A2

ln
1 y
Z
A1

0.0893(0.275 x10 4 ) 1 0.25

=
ln 1 0.75
0.2

kmol
= 1.349 x 10 5 2
m . sec

CD AB

Rate of diffusion = 1.349 8 10 5 (0.5 x 10 2) 2

= 1.059 Kmol / s
= 3.814 mol/hr

1.5.4 Diffusion into an infinite standard medium :

Here we will discuss problems involving diffusion from a spherical particle into an
infinite body of stagnant gas. The purpose in doing this is to demonstrate how to set
up differential equations that describe the diffusion in these processes. The
solutions, obtained are only of academic interest because a large body of gas in
which there are no convection currents is unlikely to be found in practice. However,
the solutions developed here for these problems actually represent a special case of
the more common situation involving both molecular diffusion and convective mass
transfer.

FDE 312- PART1: MOLECULAR DIFFUSION-27

a) Evaporation of a spherical Droplet:

As an example of such problems, we shall consider the evaporation of spherical
droplet such as a raindrop or sublimation of naphthalene ball. The vapor formed at
the surface of the droplet is assumed to diffuse by molecular motions into the large
body of stagnant gas that surrounds the droplet.
Consider a raindrop, as shown in figure. At any moment, when the radius of the drop
is r 0 , the flux of water vapor at any distance r from the center is given by
+ y A (N A + N B )
dr
Here N B = 0 (since air is assumed to be stagnant)
Therefore,
d yA
N A = C D AB
+ yA NA
dr
Rearranging,
C D AB d y A
__________ (1)
NA =
1 y A d r
d yA

N A = C D AB

The flux N A is not constant, because of the spherical geometry; decreases as the
distance from the center of sphere increases. But the molar flow rate at r and r + r
are the same.
This could be written as,
AN A = AN A
r

__________ (2)

r + r

Where

A = surface area of sphere at r or r + r.

Substituting for A = 4 r 2 in equation (2),
4 r 2 N A

4 r 2 N A

r + r

=0

or

lim

r2NA

r2NA

r 0

r + r

=0

d 2
r NA = 0
dr
Integrating,

as

r 2 N A = constant

__________ (3)

__________ (4)

From equation (4), r 2 N A = r 0 N A 0

2

Substituting for N A from equation (1),

FDE 312- PART1: MOLECULAR DIFFUSION-28

 r 2 C D AB d y A
= r 02 N A 0
dr
1 y A
r02 N A 0

dr

= C D AB

d yA

__________ (5)

1 y A

Boundary condition :
At r = r 0
y A = y AS
And
At r =
y A = y A
Therefore equation (5) becomes,

1
r 02 N A 0 = C D AB ln (1 y A )
r r0

y A
y AS

Simplifying,
1 y A

__________ (6)
ln
1 y
r0
A
S

Time required for complete evaporation of the droplet may be evaluated from
making mass balance.
N A0 =

C D AB

Moles of water diffusing moles of water leaving the droplet

=
unit time
unit time

4 r02 N A 0 =

d 4

r03 L
dt 3
M A
2 L d r0
= 4 r0
MA dt

__________ (7)

Substituting for N A0 from equation (6) in equation (7),

C D AB 1 y A L d r0
=
__________ (8)
ln
1 y AS M A d t
r0

Initial condition :
When t = 0 r 0 = r 1
Integrating equation (8) with these initial condition,
t
0
L
1
1
0 d t = M A C D AB 1 y A r r0 d r0
1
ln
1 y AS

r1
1
__________ (9)
t= L
M A 2 C D AB 1 y A

ln
1 y
A
S

Equation (9) gives the total time t required for complete evaporation of spherical
droplet of initial radius r 1 .
FDE 312- PART1: MOLECULAR DIFFUSION-29

b) Combustion of a coal particle:

The problem of combustion of spherical coal particle is similar to evaporation
of a drop with the exception that chemical reaction (combustions) occurs at the
surface of the particle. During combustion of coal, the reaction
C+O2
CO 2
cccurs. According to this reaction for every mole of oxygen that diffuses to the
surface of coal (maximum of carbon), react with 1 mole of carbon, releases 1 mole of
carbon dioxide, which must diffuse away from this surface. This is a case of equimolar
counter diffusion of CO 2 and O 2 . Normally air (a mixture of N 2 and O 2 ) is used for
combustion, and in this case N 2 does not takes part in the reaction, and its flux is
zero. i.e. N N 2 = 0 .

The molar flux of O 2 could be written as

d yO2
N O 2 = C D O 2 gas
+ y O 2 N O 2 + N CO 2 + N N 2 __________ (1)
dr
where
D O 2 gas is the diffusivity of O 2 in the gas mixture.

Since N N 2 = 0 , and from stoichiometry N O 2 = N CO 2 , equation (1) becomes

N O 2 = C D O 2 gas

d yO2

__________ (2)
dr
For steady state conditions,
d
__________ (3)
r 2 N O2 = 0
dr
Integrating,
__________ (4)
r 2 N O 2 = constant = r 02 N O 2 s

Where r 0 is the radius of coal particle at any instant, and N O 2 s is the flux of O 2 at the
surface of the particle.
Substituting for N O 2 from equation (2) in equation (4),
r 2 C D O 2 gas

d yO2
dr

= r02 N O 2 s

__________ (5)

Boundary condition :
At r = r0
yO2 = yO2 s
And

At r =

yO2 = yO2

With these boundary condition, equation (5) becomes

2
0

r N A0

dr
r r 2 = C D O 2 gas
0

y O2

d y

O2

y O2 s

FDE 312- PART1: MOLECULAR DIFFUSION-30

which yields

N O2 s =

C D O 2 gas
r0

(y

O2 s

yO2

__________ (6)

For fast reaction of O 2 with coal, the mole fraction of O 2 at the surface of particle iz
zero. (i.e.,) y O 2 s = 0 .
And also at some distance away from the surface of the particle
y O 2 = y O 2 = 0.21 (because air is a mixture of 21 mole % O 2 and 79 mole % N 2 )
With these conditions, equation (6) becomes,
0.21 C D O 2 gas
____________ (7)
N O2 s =
r0

Example 3.6. A sphere of naphthalene having a radius of 2mm is suspended in a large

volume of shell air at 318 K and 1 atm. The surface pressure of the naphthalene can
be assumed to be at 318 K is 0.555 mm Hg. The D AB of naphthalene in air at 318 K is
6.92 x 10 6 m 2/s. Calculate the rate of evaporation of naphthalene from the surface.
Calculation
Steady state mass balance over a element of radius r and r + r leads to
SNA SNA
r

r+ r

= 0 ---------------------------- (1)

where S is the surface are (= 4 r 2)

dividing (1) by Sr, and taking the limit as r approaches zero, gives:

d r 2N A

)=0

dr
Integrating r 2 N A = constant (or) 4 r 2 N A = constant
We can assume that there is a film of naphthalene vapor / air film around
naphthalene through which molecular diffusion occurs.
Diffusion of naphthalene vapor across this film could be written as,
N A = CD AB

+ y A (N A + N B )
dr
N B = 0 (since air is assumed to be stagnant in the film)
d yA

FDE 312- PART1: MOLECULAR DIFFUSION-31

N A = CD AB

dr

+ yA NA

yA

1 y A

d ln (1 y A )

N A = CD AB

N A = CD AB

d yA

d
dr

dr

W A = Rate of evaporation = 4 r 2 N A R = constant.

WA =
WA

4 r 2 CD AB d (ln (1 y A ))
dr

dr

= 4 D AB C d ln (1 y A )

Boundary condition:
yA =

At r = R
At r =

Therefore W A

dr
= 4 D AB C
r2

0.555
= 7.303 x10 4
760
ln (1 y A ) = - 7.3 x 10 4
y A = 0 ln (1-y A ) = 0

d [ln (1 y ) ]
0

7.3 *10 4

1
0
W A = 4 D AB C ln (1 y A ) 7.3 x10 4
r R
1
W A 0 + = 4 D AB C 0 + 7.3 x 10 4
R
W A = 4 R D AB C ( 7.3 x 10 4 )
P
1.01325 x10 5
C=
=
RxT
8314 x318
= 0.0383 kmol/m 3

Initial rate of evaporation:

Therefore W A = 4 x 3.142 (2 x 10 3 )( 6.92 x 10 6 ) 0.0383 ( 7.3 x10 4 )
= 4.863 x 10 12 kmol/s
= 1.751 x 10 5 mol/hr.

FDE 312- PART1: MOLECULAR DIFFUSION-32

3.5.5 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,


M av
a) For steady state diffusion of A through non diffusivity B:
N A = constant , N B = 0
NA=

D AB
(x A1 x A 2 )
z x BM M av

where Z = Z 2 Z 1 , the length of diffusion path; and

X B 2 X B1
X BM =

X
ln B 2

X
B1

b) For steady state equimolar counter diffusion :

N A = - N B = const
NA=

D AB
Z

(C

A1

D AB
(x A1 x A 2 )
Z M av

C A2 ) =

Example 3.7. Calculate the rate of diffusion of butanol at 20C under unidirectional
steady state conditions through a 0.1 cm thick film of water when the concentrations
of butanol at the opposite sides of the film are, respectively 10% and 4% butanol by
weight. The diffusivity of butanol in water solution is 5.9 x 10 6 cm 2/s. The densities
of 10% and 4% butanol solutions at 20C may be taken as 0.971 and 0.992 g/mL
respectively. Molecular weight of Butanol (C 4 H 9 OH) is 74, and that of water 18.
Calculations
For steady state unidirectional diffusion,
NA =

D AB
z

(x

A1

x A2 )

x B , lm

where C is the average molar density.

=
M avg

FDE 312- PART1: MOLECULAR DIFFUSION-33

Conversion from weight fraction the Mole fraction:

(0.1 74)

x A1 =

= 0.026

(0.1 74 + 0.9 18)

(0.04 74)
x A2 =
= 0.010
(0.04 74 + 0.96 18)

Average molecular weight at 1 & 2:

1
= 19.47 kg kmol
(0.1 74 + 0.9 18)
1
M2 =
= 18.56 kg kmol
(0.04 74 + 0.96 18)
M1 =

( 1 M 1 + 2 M 2 )

=
2
M avg
0.971 19.47 + 0.992 18.56
=
2
= 0.0517 gmol / cm 3
= 51.7 kmol/m 3
x B ,lm =

x B 2 x B1

ln (x B 2 x B1 )

(1 x ) (1 x )
A2

A1

1 x A2

ln
1 x
A1

(1 0.01 ) (1 0.026 )
(i.e.) x B ,lm =
1 0.01
ln

1 0.026
0.016
=
= 0.982
0.0163
D (x A1 x A 2 )
Therefore N A = AB
x B , lm
2 M avg

(5.9 x10 6 )(10 4 )(51.7) (0.026 0.010 )

x
0.982
0.1x10 2
kmol
= 4.97 *10 7 2
m sec
gmol
= 1.789 2
m .hr.

FDE 312- PART1: MOLECULAR DIFFUSION-34

= 1.789 x 74

= 132.4

g
m . hr.
2

g
m . hr.
2

Mass diffusion with homogeneous chemical reaction:

Absorption operations involve contact of a gas mixture with a liquid and preferential
dissolution of a component in the contacting liquid. Depending on the chemical
nature of the involved molecules, the absorption may or may not involve chemical
reaction.
The following analysis illustrates the diffusion of a component from the gas phase
into the liquid phase accompanied by a chemical reaction in the liquid phase.
Consider a layer of absorbing medium (liquid)
At the surface of the liquid, the composition of A is CA 0 . The thickness of the film, is
so defined, that beyond this film the concentration of A is always zero ; that is C A =
0. If there is very little fluid motion within the film,
N A = D AB

dCA
dz

CA
C

(N

+NB)

____________ (1)

If concentration of A in the film, C A is assumed small, equation (1) becomes

dCA
____________ (2)
N A = D AB
dz
The molar flux N A changes along the diffusion path. This change is due to the
reaction that takes place in the liquid film. This changes could be written as
d
(N A ) r A = 0
____________ (3)
dz
where r A is the rate of disappearance of A. For a first order reaction,
k
A

B
rA = k C A

____________ (4)

with the substitution from equation (4) and (2) in equation (3),
dCA
d
+ kCA = 0
D AB
dz
d z
For constant Diffusivity,

FDE 312- PART1: MOLECULAR DIFFUSION-35

 D AB

d 2CA
dz2

+ kCA = 0

____________ (5)

which is a second order ordinary differential equation. The general solution to this
equation is

C A = C 1 cos h

D AB

z + C 2 sin h

D AB

z _______ (6)

The constants of this equation can be evaluated from the boundary conditions:
at
Z=0
C A = C A0
And at
Z=
C A = 0.
The constant C 1 is equal to C A0 , and C 2 is equal to

C A0

tan h

D AB

with this

substitution equation (6) becomes,

C A = C A 0 cos h

D AB

C A 0 sin h k
z
D
AB

_______ (7)
z

tan h k
z
D AB

This equation gives the variation of concentration of A with z (i.e concentration

profile of A in the liquid). The molar flux at the liquid surface can be determined by
differentiating equation (7), and evaluating the derivative
dCA
dz

at z = 0

Differentiating C A with respect to z,

dCA

= C A0

sin h

C A0

D AB

cos h

D AB

tan h k
D AB

Substituting z = 0 in equation (8) and from equation (2),

D
D AB C A 0
AB

NA
=
____________ (9)
Z =0

tan h
D AB

dz

D AB

D AB

z
______ (8)

FDE 312- PART1: MOLECULAR DIFFUSION-36

For absorption with no chemical reaction, the flux of A is obtained from equation (2)
as
D AB C A 0
____________ (10)
NA=

which is constant throughout the film of liquid. On comparison of equation (9) and
(10), it is apparent that the term

k D tan h k D
AB
AB

shows the influence of the chemical reactions. This terms a dimensionless quantity, is
often called as Hatta Number.

3.5.7 Diffusion in solids

In certain unit operation of chemical engineering such as in drying or in absorption,
mass transfer takes place between a solid and a fluid phase. If the transferred species
is distributed uniformly in the solid phase and forms a homogeneous medium, the
diffusion of the species in the solid phase is said to be structure independent. In this
cases diffusivity or diffusion coefficient is direction independent.
At steady state, and for mass diffusion which is independent of the solid matrix
structure, the molar flux in the z direction is :
N A = D AB

dCA

= constant , as given by Ficks law.

dz
Integrating the above equation,
NA =

D AB (C A1 C A 2 )

z
which is similar to the expression obtained for diffusion in a stagnant fluid with no
bulk motion (i.e. N = 0).
Diffusion in process solids:
In some chemical operations, such as heterogeneous catalysis, an important factor,
affecting the rate of reaction is the diffusions of the gaseous component through a
porous solid. The effective diffusivity in the solid is reduced below what it could be in
a free fluid, for two reasons. First, the tortuous nature of the path increases the
distance, which a molecule must travel to advance a given distance in the solid. Sond,
the free cross stional area is restricted. For many catalyst pellets, the effective

FDE 312- PART1: MOLECULAR DIFFUSION-37

diffusivity of a gaseous component is of the order of one tenth of its value in a free
gas.
If the pressure is low enough and the pores are small enough, the gas molecules will
collide with the walls more frequently than with each other. This is known as
Knudsen flow or Knudsen diffusion. Upon hitting the wall, the molecules are
momentarily absorbed and then given off in random directions. The gas flux is
reduced by the wall collisions.
By use of the kinetic flux is the concentration gradient is independent of pressure ;
whereas the proportionality constant for molecular diffusion in gases (i.e. Diffusivity)
is inversely proportional to pressure.
Knudsen diffusion occurs when the size of the pore is of the order of the mean free
path of the diffusing molecule.
3.6 Transient Diffusion
Transient processes, in which the concentration at a given point varies with time, are
referred to as unsteady state processes or time dependent processes. This variation
in concentration is associated with a variation in the mass flux.
These generally fall into two categories:
i)
the process which is in an unsteady state only during its initial startup,
and
ii)
the process which is in a batch operation throughout its operation.
In unsteady state processes there are three variables-concentration, time, and
position. Therefore the diffusion process must be described by partial rather than
ordinary differential equations.
Although the differential equations for unsteady state diffusion are easy to establish,
most solutions to these equations have been limited to situations involving simple
geometries and boundary conditions, and a constant diffusion coefficient.
Many solutions are for one-directional mass transfer as defined by Ficks sond law of
diffusion :
CA
t

= D AB

2 C A
z2

__________ (1)

This partial differential equation describes a physical situation in which there is no

bulkmotion contribution, and there is no chemical reaction. This situation is
FDE 312- PART1: MOLECULAR DIFFUSION-38

encountered when the diffusion takes place in solids, in stationary liquids, or in

system having equimolar counter diffusion. Due to the extremely slow rate of
diffusion within liquids, the bulk motion contribution of flux equation (i.e., y A N i )
approaches the value of zero for dilute solutions ; accordingly this system also
satisfies Ficks second law of diffusion.
The solution to Ficks second law usually has one of the two standard forms. It may
appear in the form of a trigonometric series which converges for large values of time,
or it may involve series of error functions or related integrals which are most suitable
for numerical evaluation at small values of time. These solutions are commonly
obtained by using the mathematical techniques of separation of variables or Laplace
transforms.

FDE 312- PART1: MOLECULAR DIFFUSION-39