Mass Transport

EKC314:TRANSPORT PHENOMENA
Core Course for

B.Eng.(Hons.)-Chemical Engineering
Semester I (2014/2015)
Mohamad Hekarl Uzir, DIC.MSc.,PhD.(London)-chhekarl@usm.my
School of Chemical Engineering

Engineering Campus, Universiti Sains Malaysia
Seri Ampangan, 14300 Nibong Tebal
Seberang Perai Selatan, Penang
EKC314-SCE p. 1/57
Mass Transport
Diffusivity and the Mechanisms of Mass Transport:

The movement of one chemical species, A through a
binary mixture of A and B due to a concentration
gradient of A is described by Ficks Law of diffusion.
Ficks Law is governed by the diffusivity constant, D in
the form given by;
m
Ay
xA0 0
= DAB
A
Y
which can then be written as;
jAy
dxA
= DAB
dy
EKC314-SCE p. 2/57
Diffusivity and the Mechanisms of

Mass Transport
Ficks Law for Binary Diffusion (Molecular Mass Transport)

The term D is closely dependance on:
temperature difference
pressure difference
Consider a thin horizontal plate of area A and
thickness Y . (to be discussed during lecture)
EKC314-SCE p. 3/57

Mass Transport

The given equation is the 1-dimensional form of
Ficks first law of diffusion
It is valid for any binary solid, liquid or gas solution,
provided that jAy is defined as the mass flux relative to
the mixture velocity, vy .
During the operation, component A (gas) moves rather
slowly with a very small concentration. thus, vy is
negligibly different from 0, which is governed by;
vy = A vAy + B vBy
EKC314-SCE p. 4/57

Mass Transport

v is an average value with vA and vB , i.e. the mass
average velocity
The species velocity vA is not the instantaneous
molecular velocity of a molecule of A, but it is the
arithmetic average velocities of all the molecules of A
within a tiny volume element.
The mass flux is defined as;
jAy = A (vAy vy )
EKC314-SCE p. 5/57

Mass Transport

Similarly with the mass flux of component B, which
derivation leads into a conclusion that;
DAB = DBA
For the pair A-B, there is only ONE diffusivity with the
function of pressure, temperature and composition.
EKC314-SCE p. 6/57

Mass Transport

The mass diffusivity can be correlated in the form
similar to that of the momentum and thermal diffusivity
as the Schmidt number;
Sc =
=
DAB
DAB
For gas mixture, Sc number: 0.2 to 3.0.
For liquid mixture, Sc number: 40, 000
EKC314-SCE p. 7/57

Mass Transport
Temperature and Pressure Dependence of Diffusivities

For binary gas mixture at low pressure, DAB is;
1. inversely proportional to the pressure
2. increased with the increase of temperature
3. almost independent of the composition for the given
gas pair
An equation developed by combining the kinetic theory
and corresponding-states argument is given by;
pDAB
1
3
(pcA pcB ) (TcA TcB )
5
12
1
MA
1
MB
12 = a
TcA TcB
b
EKC314-SCE p. 8/57

Mass Transport
Temperature and Pressure Dependence of Diffusivities

Upon data analysis and correlation, the dimensionless
constants obtained are:
1. for non-polar gas pair: a = 2.745 104 and
b = 1.823 (excluding He and H2 )
2. for pairs consisting of H2 O and a non-polar gas:
a = 3.640 104 and b = 2.334
If the gases A and B are non-polar and their
Lennard-Jones parameters are known, the
kinetic-theory method will give better accuracy.
EKC314-SCE p. 9/57

Mass Transport
Theory of Gas Diffusion in Gases at Low Density

For self-diffusion, DAA the correlation is given by;
(cDAA )c = 2.96 106
1
1
+
MA MA
12
2/3
pcA
1/6
TcA
The above equation SHOULD NOT be used for He or

H2 isotopes.
For binary-diffusion, the correlation expanded into the
form of;
(cDAB )c = 2.96 106
1
1
+
MA MB
12
(pcA pcB )1/3

(TcA TcB )1/12
EKC314-SCE p. 10/57

Mass Transport

Some results of the kinetic theory of gases were given
previously as;
the mean molecular speed relative to v;
r
8T
u =
m
the wall collision frequency per unit area in a
stationary gas;
1
u
Z = n
4
EKC314-SCE p. 11/57

Mass Transport

Some results of the kinetic theory of gases were given
previously as;
the mean free path;
1
=
2d2 n
EKC314-SCE p. 12/57

Mass Transport
Theory of Diffusion in Binary Liquids

The theory starts with the development of the
hydrodynamic-theory from the Nernst-Einstein
equation given by;
DAB
uA
= T
FA
where uA /FA is the mobility of a particle A

[steady-state velocity of the particle attained under the
action of a unit force].
EKC314-SCE p. 13/57

Mass Transport

By applying the creeping flow equation of motion, with
A is in spherical shape and slip condition applies, the
final equation expands into;

uA
3B + RA AB
1
=
FA
2B + RA AB 6B RA
at the fluid-solid interface.
EKC314-SCE p. 14/57

Mass Transport

The limiting cases of AB are of particular interest to
the system:
1. AB = (no-slip condition): At the fluid-solid
interface, the previous equation reduces into
Stokess Law in the form given by;
DAB B
1
=
T
6RA
EKC314-SCE p. 15/57

Mass Transport

the system:
1. OR usually called the Stokes-Einstein equation. It
can be applied to the diffusion of a very large
spherical molecules in solvents of low molecular
weight and to suspended particles. It has also been
used to estimate the shapes of protein molecules.
2. AB = 0 (complete slip condition): Similarly, the
equation at the fluid-solid interface reduces into;
DAB B
1
=
T
4RA
EKC314-SCE p. 16/57

Mass Transport

the system:
2. If the molecules A and B are identical,
(self-diffusion) and they can be assumed to form
cubic lattice with adjacent molecules, thus;
DAA A
1
=
T
2
A
N
VA
! 13
EKC314-SCE p. 17/57

Mass Transport

The formulae derived above only apply to dilute
solution of A and B.
EKC314-SCE p. 18/57
Concentration Distributions in Solids

and in Laminar Flow
Shell Mass Balances; Boundary Conditions
1. The law of conservation of mass of species A in a
binary system can be written over the volume of the
shell as; (to be discussed)
2. A chemical species, A may leave or enter a system by
diffusion [molecular motion and convection], these are
included in the term, NA .
3. Species A may also be produced or consumed by
homogeneous chemical reactions.
4. When the overall balance is complete, the shell is then
made into an infinitesimally small thickness.
5. A system of differential equation is generated either in
the form of mass or molar flux.
EKC314-SCE p. 19/57

and in Laminar Flow
6. The integration of the differential equation leads to a
number of constants which requires boundary
conditions for them to be determined.
(a) the concentration at surface can be specified:
xA = xA0 .
(b) mass flux at the surface can be specified:
NAz = NA0 . If the ratio of NA0 /NAz is known, the
concentration gradient is already known.
(c) for diffusion occurs in a solid, at the solid surface,
substance A is lost to the surrounding stream due
to;
NA0 = kc (cA0 CAb )
EKC314-SCE p. 20/57

and in Laminar Flow
6. The integration of the differential equation leads to a
number of constants which requires boundary
conditions for them to be determined.
(d) the rate of chemical reaction at the surface can be
specified.
EKC314-SCE p. 21/57

and in Laminar Flow
Diffusion Through a Stagnant Gas Film
Consider a diffusion system where a liquid A is
evaporating into gas A. Assuming that the liquid
level is maintained at z = z1 .
At the liquid-gas interface, the gas phase concentration
of A (in mole fraction) is xA1 . This is the vapour
pvap
pressure of A divided by the total pressure, Ap .
(Assuming that gas A and liquid B obey the ideal
gas mixture and that the solubility of gas B in
liquid A is negligible)
A stream of gas mixture A-B with concentration xA2
flows past the top of the tube, maintaining the mole
fraction of A at xA2 for z = z2 .
EKC314-SCE p. 22/57

and in Laminar Flow
System must be kept at constant pressure and
temperature and both gases A and B are assumed to
be ideal.
Neglecting the effect of dependency of gas velocity (of
the z-component) with respect to the radius of the
container/cylinder.
At the steady state a balance equation of the form
below is obtained;
NAz
xA
= cDAB
+ xA (NAz + NBz )
z
EKC314-SCE p. 23/57

and in Laminar Flow
When NBz = 0, solving for NAz resulted into;
NAz
cDAB dxA
=
1 xA dz
At a steady-state condition, for every increment of z,

the amount of A entering at plane z equals to the
amount of A leaving at plane z + z, which leads to;
SNAz |z SNAz |z+z = 0
where S is the cross-sectional area of the
column/cylinder.
EKC314-SCE p. 24/57

and in Laminar Flow
Division by Sz and taking limit as z 0 leads to;
dNAz
=0
dz
Combining with the previous equation gives;

d
cDAB dxA
=0
dz 1 xA dz
EKC314-SCE p. 25/57

and in Laminar Flow
For an ideal gas mixture;
p = cRT
and for gases, DAB is nearly independent of the
composition, thus;

d
1 dxA
=0
dz 1 xA dz
Upon integration gives;
1 dxA
= C1
1 xA dz
EKC314-SCE p. 26/57

and in Laminar Flow
With further integration leads to;
ln (1 xA ) = C1 z + C2
By replacing C1 with ln K1 and C2 with ln K2 ,
reduces the equation into;
1 xA = K1z K2
EKC314-SCE p. 27/57

and in Laminar Flow
Using boundary conditions:
i. B.C. 1: at z = z1 , xA = xA1
ii. B.C. 2: at z = z2 , xA = xA2
the equation becomes;

1 xA
1 xA1
1 xA2
1 xA1
zzz
1
z
2
The profile for gas B can be determined using

xB = 1 xA
The slope of the profile, dxA /dz is not constant
although NAz is.
EKC314-SCE p. 28/57

and in Laminar Flow
The equation determined above can be used to obtain
the average values and mass fluxes at surfaces.
The average concentration of B in the region between
z1 and z2 can be found using;

R 1 xB2
R z2 xB
xB2 1
( )dz
( ) d
( xB1 )
xB,avg
z1 xB1
0 xB1
= R z2
=
=
R1
xB2
xB1
ln ( xB1 )
dz
d
z1
0
0
where = (z z1 )/(z2 z1 ) or can be rewritten as;

xB,avg
xB2 xB1
=
ln xxB2
B1
EKC314-SCE p. 29/57

and in Laminar Flow
With the previous equation, the mass transfer at the
liquid-gas interface (rate of evaporation) can be
obtained using;

cDAB dxA
cDAB dxB

=
=
NAz

1 xA1 dz
xB1 dz
z=z1
z=z1
cDAB
ln
=
z2 z1
xB2
xB1
z=z1
EKC314-SCE p. 30/57

and in Laminar Flow
By combining the mass transfer equation with that of
the logarithmic mean given by, xB,avg leads to;

NAz
z=z1
cDAB
=
(xA1 xA2 )
(z2 z1 )(xB )ln
EKC314-SCE p. 31/57

and in Laminar Flow
Diffusion with a Heterogeneous Chemical Reaction
Involved solid catalyst with either gas or liquid phase
reactant.
Reaction only occurs at the catalyst surface when
reactant(s) diffuses towards the surface (external
diffusion) OR diffuses into the porous catalyst (for
internal diffusion)
For a reaction involving a component A (reactant)
producing component B (product), component A needs
to diffuse into the surface of the catalyst at which the
reaction will occur and the product B formed from the
reaction will diffuse back out. The reaction is assumed
to occur instantaneously.
EKC314-SCE p. 32/57

and in Laminar Flow
Also assuming that the gas film is isothermal at this
point.
For a reaction given by;
2A B
at steady-state condition;
NBz
1
= NAz
2
EKC314-SCE p. 33/57

and in Laminar Flow
The substituted equations give;
NAz
cDAB dxA
=
1 12 xA dz
Consider a thin slab of thickness z in the gas film.

The balanced equation gives;
dNAz
dz
EKC314-SCE p. 34/57

and in Laminar Flow
Substitute with the above equation leads to;

d
1
dxA
=0
1
dz 1 2 xA dz
Upon integration w.r.t z resulted into;
1
2 ln (1 xA ) = C1 z + C2 = (2 ln K1 )z (2 ln K2 )
2
EKC314-SCE p. 35/57

and in Laminar Flow
Using boundary conditions of:
1. B.C. 1: at z = 0 and xA = xA0
2. B.C. 2: at z = and xA = 0
Leads into;
1
1
1 z
(1 xA ) = (1 xA0 )
2
2
which then gives the molar flux of reactant through the
film;

2cDAB
1
NAz =
ln
1 12 xA0
EKC314-SCE p. 36/57

and in Laminar Flow
Diffusion with a Homogeneous Chemical Reaction
Consider a reaction involving component A (gas
phase) and B (liquid phase) with reaction following,
A(g) + B(l) AB(l)
Assuming that the formation of AB does not affect the
diffusion process (pseudo-binary assumption) and
upon mass balance on species A over a thickness z
of the liquid phase;

NAz z S NAz z+z S k1 cA Sz = 0
where k1 is the first order rate constant for the

decomposition of A, with S as the cross-sectional area
of the liquid.
EKC314-SCE p. 37/57

and in Laminar Flow
The division by Sz and taking limit z 0 gives;
dNAz
+ k1 cA = 0
dz
For a very small concentration of A, the by
approximation,
NAz
dcA
= DAB
dz
EKC314-SCE p. 38/57

and in Laminar Flow
And therefore leads to;
d 2 cA
DAB 2 k1 cA = 0
dz
The above equation can be solved using the boundary
conditions:
1. B.C. 1: at z = 0 and cA = cA0
2. B.C. 2: at z = L and NAz = 0 OR dcdzA = 0
EKC314-SCE p. 39/57

and in Laminar Flow
With the dimensionless variable as;
d2
2
=0
2
d
the dimensionless variables include:
1. dimensionless concentration: =
2. dimensionless length: =
cA
cA0
z
L
3. dimensionless Thiele Modulus: =
k1 L2
DAB
EKC314-SCE p. 40/57

and in Laminar Flow
Using the necessary boundary conditions:
1. B.C. 1: at = 0, = 1
2. B.C. 2: at = 1, d
=0
d
which then gives the solution of the form of;
= C1 cosh + C2 sinh
Solving for the constants leads to;
cosh [(1 )]
cosh cosh sinh sinh
=
=
cosh
cosh
EKC314-SCE p. 41/57

and in Laminar Flow
Substitute back to the original notation resulted into;
q
k1 L2
z
cosh
(1
)
cA
DAB
L
q
=
cA0
k1 L2
cosh DAB
The above equation can be used to determine the
average concentration in the liquid phase;
cA,avg
=
cA0
RL
cA
(
)dz
tanh
0 cA0
=
RL
dz
0
EKC314-SCE p. 42/57

and in Laminar Flow
The molar flux at the plane z = 0 can also be found
using;

cA0 DAB
dcA

tanh
NAz
= DAB
=

dz z=0
L
z=0
EKC314-SCE p. 43/57

and in Laminar Flow
Diffusion into a Falling Liquid Film (Gas Absorption)
Consider a system of forced-convection mass transfer
in which viscous flow and diffusion occur under such
conditions that the velocity field can be considered as
virtually unaffected by the diffusion.
Specifically, consider consider the absorbtion of gas A
by a laminar falling film of liquid B.
Material A is only slightly soluble in B, so that the
viscosity of the liquid is unaffected.
The diffusion also takes place very slowly in the liquid
film that component A (gas) will not penetrate very far
into the film (the penetration distance will be small in
comparison with the film thickness)
EKC314-SCE p. 44/57

and in Laminar Flow
Let the system is the absorption of O2 in H2 O.
Consider the momentum transfer of the falling film
(refer to momentum transfer example), which resulted
into the velocity profile in z-direction given by;

x 2
vz (x) = vmax 1
ignoring the end effect
EKC314-SCE p. 45/57

and in Laminar Flow
Consider mass balance on component A that changes
w.r.t thickness x as well as z which resulted into;

NAz W x NAz
W x
z
z+z

+NAx W z NAx
W z = 0
x
x+x
Dividing the above equation with W xz and the

usual limiting process as volume element becomes
0 gives;
NAz NAx
+
=0
z
x
EKC314-SCE p. 46/57

and in Laminar Flow
But, NAz and NAx are given by;
NAz
cA
+ xA (NAz + NBz ) cA vz (x)
= DAB
z
NAx
cA
cA
= DAB
+ xA (NAx + NBx ) DAB
x
x
and
respectively.
EKC314-SCE p. 47/57

and in Laminar Flow
Upon substitution gives;

x 2 c
2 cA
A
vmax 1
= DAB
z
x2
with boundary conditions;
1. B.C. 1: at z = 0, cA = 0
2. B.C. 2: at x = 0, cA = CA0
A
3. B.C. 3: at x = , c
=0
x
EKC314-SCE p. 48/57

and in Laminar Flow
The first B.C.: the film consists of pure B at the top
(z = 0)
The second B.C.: at the liquid-gas interface, the
concentration of A is determined by the solubility of A
in B (that is cA0 )
The third B.C.: A cannot diffuse through the solid wall
Due to this reasons, the equation needs to be modified
such that the B.C. is valid thus the new equation
becomes;
cA
2 cA
vmax
= DAB
z
x2
EKC314-SCE p. 49/57

and in Laminar Flow
With the new boundary conditions;
1. B.C. 1: at z = 0, cA = 0
2. B.C. 2: at x = 0, cA = CA0
3. B.C. 3: at x = , cA = 0
By applying the method of combination of variables
leads to;
cA
2
=1
cA0
x
4DAB z
vmax
exp ()2 d
EKC314-SCE p. 50/57

and in Laminar Flow
Or it can also be written in the form of;
x
x
cA
= 1 erf q
= erfc q
cA0
4DAB z
4DAB z
vmax
vmax
This will give the local mass flux at the gas-liquid

interface using;
r

cA
DAB vmax

NAx
= DAB
= cA0

x x=0
z
x=0
EKC314-SCE p. 51/57

and in Laminar Flow
Then the total molar flow of A across the surface at
x = 0 is given by;
WA =
= W LcA0

NAx
x=0
dzdy
4DAB vmax
L
EKC314-SCE p. 52/57

and in Laminar Flow
Diffusion into a Falling Liquid Film (Solid Dissolution)
Consider a liquid B flowing in laminar motion down a
vertical wall.
The film begins far enough up the wall such that vz
depends only on y for z 0.
For 0 0 L, the wall is made of a species A that is
slightly soluble in B.
For a short distances downwards, species A will not
diffuse very far into the falling film.
A is present only in a very thin boundary layers near
the solid surface.
EKC314-SCE p. 53/57

and in Laminar Flow
The diffusing A molecules will experience a velocity
distribution similar to that of the falling film next to the
wall at y = 0 where;

2
2
g cos
x
1
vz =
2
When cos = 1 and x = y, thus;

2
2
2
g
y
g
y
y 2
vz =
1
=
2
EKC314-SCE p. 54/57

and in Laminar Flow
At and adjacent to the wall;
y 2
y
therefore, the velocity vz ca be approximated to;

vz =
EKC314-SCE p. 55/57
Equations of Change for

Multicomponent Systems
Equation of Continuity for a Multicomponent Mixture:

To establish the equation of continuity for various
species in a multicomponent mixture (using mass
balance)
To obtain diffusion equations (in various forms) by
inserting the mass flux equation of continuity
To combine all equations of change for mixture for
problem solving.
EKC314-SCE p. 56/57
Equations of Change for

Multicomponent Systems
Equation of Continuity for a Multicomponent Mixture:

i. rate of increase of mass, in the volume element,
xyz
t
ii. rate of addition of mass, across face at x, nx |x yz
iii. rate of removal of mass, across face at x + x,

nx |x+x yz
iv. rate of production of mass, by chemical reaction,

r xyz
EKC314-SCE p. 57/57

Mass Transport

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EKC314:TRANSPORT PHENOMENA

Core Course for

School of Chemical Engineering

Diffusivity and the Mechanisms of Mass Transport:

Diffusivity and the Mechanisms of

Ficks Law for Binary Diffusion (Molecular Mass Transport)

Diffusivity and the Mechanisms of

Ficks Law for Binary Diffusion (Molecular Mass Transport)

Diffusivity and the Mechanisms of

Ficks Law for Binary Diffusion (Molecular Mass Transport)

Diffusivity and the Mechanisms of

Ficks Law for Binary Diffusion (Molecular Mass Transport)

Diffusivity and the Mechanisms of

Ficks Law for Binary Diffusion (Molecular Mass Transport)

Diffusivity and the Mechanisms of

Temperature and Pressure Dependence of Diffusivities

(pcA pcB ) (TcA TcB )

Diffusivity and the Mechanisms of

Temperature and Pressure Dependence of Diffusivities

Diffusivity and the Mechanisms of

Theory of Gas Diffusion in Gases at Low Density

The above equation SHOULD NOT be used for He or

(pcA pcB )1/3

Diffusivity and the Mechanisms of

Theory of Gas Diffusion in Gases at Low Density

Diffusivity and the Mechanisms of

Theory of Gas Diffusion in Gases at Low Density

Diffusivity and the Mechanisms of

Theory of Diffusion in Binary Liquids

where uA /FA is the mobility of a particle A

Diffusivity and the Mechanisms of

Theory of Diffusion in Binary Liquids

Diffusivity and the Mechanisms of

Theory of Diffusion in Binary Liquids

Diffusivity and the Mechanisms of

Theory of Diffusion in Binary Liquids

Diffusivity and the Mechanisms of

Theory of Diffusion in Binary Liquids

Diffusivity and the Mechanisms of

Theory of Diffusion in Binary Liquids

Concentration Distributions in Solids

Concentration Distributions in Solids

Concentration Distributions in Solids

Concentration Distributions in Solids

Concentration Distributions in Solids

Concentration Distributions in Solids

At a steady-state condition, for every increment of z,

Concentration Distributions in Solids

Concentration Distributions in Solids

Concentration Distributions in Solids

Concentration Distributions in Solids

The profile for gas B can be determined using

Concentration Distributions in Solids

where = (z z1 )/(z2 z1 ) or can be rewritten as;

Concentration Distributions in Solids

Concentration Distributions in Solids

Concentration Distributions in Solids

Concentration Distributions in Solids

Concentration Distributions in Solids

Consider a thin slab of thickness z in the gas film.

Concentration Distributions in Solids

Concentration Distributions in Solids

Concentration Distributions in Solids

where k1 is the first order rate constant for the