CHAPTER 14

Diffusion Mass Transfer

Fundamentals

Prepared by: Prof. Dr. Ş. Birgül Tantekin-Ersolmaz

Prof. Dr. Hüsnü Atakül
 Objectives
 Understand the concentration gradient and the physical
mechanism of mass transfer
 Recognize the analogy between heat and mass transfer
 Describe the concentration at a location on mass or
mole basis, and relate the rate of diffusion to the
concentration gradient by Fick’s law
 Analyze the rate of mass diffusion with or without
homogenous reaction under steady conditions in a
stationary or non-stationary medium
 Perform a one-dimensional transient mass diffusion
analysis in a stationary medium

2
 General Considerations
 Must have a mixture of two or more
species for mass transfer to occur.
 Mass transfer is the net movement
of a species in a mixture from one
location to another as a result of
concentration difference. Mass flows from the high to
 In separation processes, the transfer the low concentration region.
takes place across an interphase
between phases.
Mechanisms of mass transfer:
slow  Molecular diffussion
rapid  Convection (bulk flow)
rapid  Eddy (turbulent)
diffusion
3
 Diffusion occurs due to driving forces
• Gradients of
 Species concentration (ordinary diffusion)
 Pressure (requires a large gradient)
 Temperature (thermal gradient)
 External forces (such as electrical field)
Bulk flow
Total molar flux of species i (Ni): (convection)

N i  molecular diffusion flux of i  eddy diffusion flux of i  xi N 

Molecular diffusion occurs in fluids that are stagnant or in laminar

or turbulent motion
Eddy diffusion occurs in fluids when turbulent motion exists

When mass transfer under turbulent flow occurs across an interface or to a solid
surface, flow is laminar near the interface and eddy diffusion is eliminated.
4
 Physical Origins of Diffusion
• Transfer is due to random
molecular motion
• Mass diffusion occurs in
liquids and solids, as well
as gases.

 Consider two species A and B at

the same T and p, but initially
separated by a partition.

 Diffusion in the direction of decreasing concentration dictates

net transport of A molecules to the right and B molecules to
the left.
 In time, uniform concentrations of A and B are achieved.
5
 Examples of Mass Transfer
Mass transfer could take place between different phases.
Examples:
 diffusion of nitrous oxides from vehicle exhausts in air.
 diffusion of dissolved O2 in air
 diffusion of helium in Pyrex
 diffusion of dissolved KMnO4 in water

6
Analogy Between Heat and Mass Transfer
We can develop an understanding of mass transfer in a short
time with little effort by simply drawing parallels between heat
and mass transfer.
Temperature vs. Concentration

• The driving force for mass transfer

is the concentration difference.
• Both heat and mass are transferred
from the more concentrated
regions to the less concentrated
ones.
• If there is no difference between
the concentrations of a species at
different parts of a medium, there
will be no mass transfer.
7
Analogy Between Heat and Mass Transfer
Conduction vs. Diffusion
Mass is transferred by conduction (called diffusion) and convection only.
dT Fourier’s law of dC A Fick’s law of
qcond  kA J A,diff   DAB A
dx heat conduction dx diffusion

DAB is the diffusion coefficient (or mass

diffusivity) of the species in the mixture
dT
CA is the concentration of the species in the qcond  kA
dx
mixture

dC A
J A,diff   DAB A
dx
8
 Analogy Between Heat and Mass Transfer
Heat Generation vs. Mass Generation
 Heat generation refers to the conversion of some form of energy such
as electrical, chemical, or nuclear energy into sensible thermal energy in
the medium.
 Some mass transfer problems involve chemical reactions that occur
within the medium and result in the generation of a species throughout.
 Therefore, species generation is a volumetric phenomenon, and the rate
of generation may vary from point to point in the medium.
 Such reactions that occur within the medium are called homogeneous
reactions and are analogous to internal heat generation.
 In contrast, some chemical reactions result in the generation of a
species at the surface as a result of chemical reactions occurring at the
surface due to contact between the medium and the surroundings.
 This is a surface phenomenon, and as such it needs to be treated as a
boundary condition. In mass transfer studies, such reactions are called
heterogeneous reactions and are analogous to specified surface heat
flux. 9
Analogy Between Heat and Mass Transfer
Heat Convection vs. Mass Convection
 Mass convection (or convective mass transfer) is the mass transfer
mechanism between a surface and a moving fluid that involves both
mass diffusion and bulk fluid motion. Fluid motion enhances mass
transfer considerably.
 In mass convection, we define a concentration boundary layer in an
analogous manner to the thermal boundary layer and define new
dimensionless numbers that are counterparts of the Nusselt and
Prandtl numbers.

qconv  hAs Ts  T 

Rate of heat convection
(Newton’s law of cooling)

N A,conv  hm As  C A,s  C A,  Rate of mass convection

hm (or sometimes shown as k) is the mass transfer coefficient, As is the

surface area, (CA,s − CA, ) a suitable concentration difference across the
concentration boundary layer. 10
 Mixture Composition
A mixture consists of two or more chemical species. The amount
of any species i may be quantified in terms of its mass density
i (kg/m3) or molar concentration Ci (kmol/m3).
total mixture concentration
mixture mass density (kg/m3)
(mixture molar density) (kmol/m3)
   i C   Ci
i
i
The mass density and molar concentration are related through
the species molecular weight, Mi (kg/kmol).

i  M i Ci
i
Mass fraction of species i: mi 

m
i
i 1

Mole fraction of species i: xi 

Ci
C
x
i
i 1
11
 Mixture of Ideal Gases

p   pi
pi
The mass fraction of species i: i 
RT i

pi Ci pi
The mole fraction of species i: Ci  xi  
RT C p
Ci = the concentration of species i
pi = partial pressure of species i
R = the universal gas constant

12
 Species Velocities
The velocity (m/s) of each component of a mixture
comprises two factors:
vi  vd  v
diffusion bulk velocity
velocity (mixture velocity)

n n
1
Average bulk velocity based on mass:
mass average velocity
v

  v  m v
i 1
i i
i 1
i i

1 n n
Average bulk velocity based on moles: v*   Ci vi   xi vi
molar average velocity C i 1 i 1

13
 Species Fluxes in Mixtures
Recall that: A flux is the amount of material
crossing a unit area normal to the direction of
transport in a given unit time. Fluxes are vectors.
Fluxes are defined for fixed or moving coordinates.

For fixed coordinates, the mass and molar fluxes of component i are:
n n
ni  i vi ,  v   ni N i  Ci vi , Cv*   N i
i 1 i 1

The diffusive mass flux and diffusive molar flux of component i relative
to mass average velocity are: (moving coordinates)

ji  i  vi  v   i vd J i  Ci  vi  v   Ci vd
The diffusive mass flux and diffusive molar flux of component i relative
to molar average velocity are: (moving coordinates)

ji*  i  vi  v*  J i*  Ci  vi  v*  14
 Species Fluxes in Mixtures
Fluxes based upon fixed and moving coordinates are related as follows:

ji  ni  i v ji*  ni  i v*

J i  N i Ci v J i*  N i Ci v*
For a binary system ( i =A, B): N   N A  N B , n  nA  nB
N A  J A  C Av N A  J A * C Av*
nA  j A   Av nA  j A *   Av*
Recall:  v  nA  nB Cv  N A  N B
1
v  nA  nB  1
v   N A  N B 
 C
Therefore: nA  j A  mA  nA  nB  nA  j A *  mA  nA  nB 

N A  J A  x A  N A  N B  N A  J A *  x A  N A  N B  15

 Species Fluxes in Mixtures
The Dilute-Solution Assumption
The component of most solutions are dilute, and several
simplification can therefore be made:

Dilute solution  Cs  Ci or xs  1  xi
This approximation is
sometimes not valid solvent solvent mole
concentration fraction

 s  i or ms  1  mi
Then: v*  vs and v  vs  v  v*
J i*  J i and N i  J i  Ci vs
• Average fluid velocity (on mass or molar basis)  solvent velocity
• The only interactions that are important are those between the solute
and the solvent (pseudo binary system) 16
 Binary Molecular Diffusion
Fick’s law of diffusion: Recall that: Molecular diffusion is the
mass movement of one species in
another.

dC A dCB
J *
A,x   DAB J *
B ,x   DBA
dx dx
binary diffusion coefficient

dx A  kmol 
J *
 CDAB  2  In vector form:
A,x
dx  m s 
j A    DAB mA
dmA  kg 
j A,x    DAB  2  J  CDAB x A
*

dx  m s  A
17
 Binary Molecular Diffusion
When there is a bulk flow (convection): Nonstationary Medium
Total flux = Diffusive flux + Convective flux

x A
N A  CDAB  x A  N A  N B  Total molar flux
z
mA
nA    DAB  mA  nA  nB  Total mass flux
z
xB mB
N B  CDBA  xB  N A  N B  nB    DBA  mB  nA  nB 
x z
For dilute solution, the diffusion coefficient is a function of temperature
and pressure, i.e. solute-solute interaction is negligible. Therefore,
diffusion coefficient is independent of the solute concentration.
For concentrated solution, solute-solute interaction become important.
Diffusion coefficient is concentration-dependent. 18
 Diffusion Coefficient
• The diffusion coefficients, in general,
are highest in gases and lowest in
solids. The diffusion coefficients of
gases are several orders of magnitude
greater than those of liquids.
• Diffusion coefficients increase with
temperature.
For gases:
32
T 32
DAB ,1 p2  T1 
DAB  or   
p DAB ,2 p1  T2 

For liquids and solids:

Empirical correlations
19
Diffusivity Relationships

20
 Summary of Equations for Total Flux
Binary Mixture in Nonstationary Media

• Molar Flux of Species A:

 
N A  CA vA  J A  CA v 
N A  J A*  CA  xA vA  xBvB 

N A  CDABxA  xA  N A  N B 

• Mass Flux of Species A:

nA   A vA  jA   A v nA  jA   A  mA vA  mBvB 

nA    DABmA  mA  nA  nB 

21
 Special Case-1: Equimolar Counter Diffusion
Molar fluxes are equal but opposite direction
N   N A  N B  0

J A*   J B *
dx A
N A  J A  CDAB
dz
dxB

N B  J B  CDBA
dz
If c, p, T and mole fraction of two
sides are constant but different:
CDAB
J *A    xA1  xA 
z  z1
CDBA
J *B    xB1  xB 
z  z1 22
 Special Case-2: Unimolecular Diffusion
Mass transfer of A through stagnant B

N B  0 and N   N A

dx A
N A  x A N A  CDAB
dz

CDAB dx A CDAB dx A
N A    Mole fraction, x

1  x A dz xB dz
bulk flow effect

23
 Special Case-3: Stationary Medium
No bulk flow (convection)
When is it approriate to neglect the convective (also called advective)
contribution to mass transfer?
When the diffusion of a very small amount of species A ocurs within a
stagnant species B, the molecular motion associated wih mass transfer
will not induce significant bulk motion of the medium. The medium can be
assumed stationary.
CDAB dx A dx A
N A    if x A  1 then N A  CDAB  J A*
bulk flow 1  x A dz dz
effect

This situation is common when one considers the difusion of a dilute

gas or liquid within a stagnant liquid or a solid host medium.

nA  j A    DAB mA Stationary medium approximation

allows a direct analogy between
conduction heat transfer and
N A  J *A  CDAB x A diffusion mass transfer. 24
 Conservation Relations
Total Mass Balance
It is established for a control volume (CV).

 Rate of mass flow  Rate of mass flow   Rate of change of mass 

   
 into the CV   out of the CV   in the CV 
dM
M in  M out   M st
dt
For a differential CV of dxdydz:
Recall that you have derived total mass balance for a
fluid in motion in Fluid Mechanics course.

    ux    u y    uz  
    
t  x y z 
 
Equation of Continuity 25
 Conservation of Mass for a Mixture
Species (Component) Mass Balance

 Moles/mass of i   Moles/mass of i 
  
entering into the CV   leaving the CV 
 Rate of production/ 
   Rate of accumulation 
 consumption of i by chemical    
reaction within the CV   of i within the CV 
 
dM A
M A,in  M A,out  M A, g   M A, st
dt
mass stored or
accumulated

26
 Steady-State Mass Transfer in One Dimension
Species Mass Balance in Rectangular Coordinates

 Moles/mass of i   Moles/mass of i 
  
 entering into the CV   leaving the CV 
 Rate of production/ 
   Rate of accumulation 
 consumption of i by chemical    
reaction within the CV   of i within CV 
 
Mass generation/consumption
For a fixed coordinate: due to reaction
N i  Ri

N i,x Ax x  N i,x Ax x   x  N i Ax  x   Ci Ax  x  Reaction rate
t
Divide by Ax  x take limit as x  0:

N i,x x  N i,x Ci 

N i,x Ci
xx
 Ni     Ni 
x t x t
27
 Steady-State Mass Transfer in One Dimension
Species Mass Balance in Rectangular Coordinates

N i,x Ci
  Ni  where N i,x  J i*,x  Ci vx
x t
For a binary system:   J *A,x  x A  N A,x
N A,x   N B,x 

For the case of stationary medium (no bulk flow): vx 

 0  N A,x  J A,x
*

J *
C A  2
CA C A
  NA 
A,x

insert Fick's law
 DAB  NA 
x t J  D *dC
A,x
dx
AB
A
x 2
t
C A d 2Ci
At steady-state: 0  DAB  NA  0
t dx 2

 2C A C A
No chemical reaction: NA  0  DAB 
x 2
t 28
 Steady-State Mass Transfer in One Dimension
Species Mass Balance in Cylindrical Coordinates

 Moles/mass of i   Moles/mass of i 
  
 entering into the CV   leaving the CV 
 Rate of production/ 
   Rate of accumulation 
 consumption of i by chemical    
reaction within the CV   of i within CV 
 

Ci
N i,r 2rL r  N i,r 2rL r r  N i 2rLr  2rLr
t
Divide by 2Lr and take limit as r  0:

Ci 1  rN i,r r  rN i,r  Ci 1   rN i,r 

  r r
  Ni    Ni
t r  r 
 t r r
In the absence of convection Ci Dij   Ci 
 r   Ni
(stationary medium), insert Fick’s law: t r r  r  29
 Steady-State Mass Transfer in One Dimension
Species Mass Balance in Spherical Coordinates

 Moles/mass of i   Moles/mass of i 
  
 entering into the CV   leaving the CV 
 Rate of production/ 
   Rate of accumulation 
 consumption of i by chemical    
reaction within the CV   of i within CV 
 

Ci
N i,r 4r 2
 N i,r 4r 2
 N i 4r r 
2
4r 2 r
r r r t
Divide by 4r and take limit as r  0:

Ci 1 
 2
r 2
N 
i ,r r  r 2
N i,r
r r

  Ni  Ci 1
 2
  r 2
N i,r 
 Ni
t r  r  t r r
 
In the absence of convection Ci Dij   2 Ci 
 2 r   Ni
(stationary medium), insert Fick’s law: t r r  r  30
General Conservation of Mass for a Mixture
Ax
Ci
xyz  N i,x yz x  N i,x yz x x
t Ay
 N i,y xz  N i,y xz
y y y

 N i,z xy z  N i,z xy z z

Az
 N i xyz
V

Divide by xyz and take limit as x, y, and z approach zero:

Ci  N i,x N i,y N i,z 

      Ni
t  x y z 
31
General Conservation of Mass for a Mixture
Ci  N i,x N i,y N i,z  in terms of molar fluxes
      Ni and mole concentration
t  x y z 
Ci
   N i N i in vector form
t
Conservation of Mass based on Molar fluxes with respect to Fixed Coordinates

Ci  N i,x N i,y N i,z 

      Ni
t  x y z 
Ci  1   rN i,r  1 N i, N i,z 
      N i
t  r 
 r r z 
Ci  1   rN i,r  1   N i, sin   1 N i, 
      Ni
t  r sin   r sin    32
 r r
General Conservation of Mass for a Mixture
i  ni,x ni,y ni,z  in terms of mass fluxes and
      ni mass concentration
t  x y z 
i
   ni  ni in vector form
t
Conservation of Mass based on Mass fluxes with respect to Fixed Coordinates

i  ni,x ni,y ni,z 

      ni
t  x y z 
i  1   rni,r  1 ni, ni,z 
      ni
t  r 
 r r z 
i  1   rni,r  1   ni, sin   1 ni, 
      ni
t  r sin   r sin   
 r r
33
 The Mass Diffusion Equation
Stationary medium (in terms of molar fluxes and mole concentration)

Rectangular   Ci    Ci    Ci  Ci

Coordinates  Dij   Dij   Dij   Ni 
x  x  y  y  z  z  t
If total concentration (C) is constant:

  xi    xi    xi  Ci

 CD    CD    CD   N 
x  x  y  y  z  z  t
ij ij ij i

Cylindrical 1   Ci  1   Ci    Ci  Ci

 ij
D r 
 2  ij
D    ij
D   N 
Coordinates r r  r  r     z  z 
i
t

1   2 Ci  1   Ci  1   Ci  Ci

 Dij r  2 2  Dij  2  Dij   Ni 
r r 
2
r  r sin      r sin      t
Spherical
Coordinates
34
 The Mass Diffusion Equation
Stationary medium (in terms of mass fluxes and mass concentration)

Rectangular   i    i    i  i

Coordinates  Dij   Dij   Dij   ni 
x  x  y  y  z  z  t
If total concentration () is constant:

  mi    mi    mi  i

  D     D     D 
 i n 
x  x  y  y  z  z  t
ij ij ij

Cylindrical 1   i  1   i    i  i

 ij
D r 
 2  ij
D    ij
D 
 i n 
Coordinates r r  r  r     z  z  t

1   2 i  1   i  1   i  i

 Dij r  2 2  Dij  2  Dij   ni 
r r 
2
r  r sin      r sin      t
Spherical
Coordinates
35
 The Mass Diffusion Equation  Stationary Medium
Special Cases

Transient with  2Ci  2Ci  2Ci N i 1 Ci  2 xi  2 xi  2 xi N i 1 xi

 2  2   or    
constant Dij: x 2
y z Dij Dij t x 2 y 2 z 2 CDij Dij t

Steady state with  2Ci  2Ci  2Ci Ni  2 xi  2 xi  2 xi Ni

 2  2   0 or  2  2  0
constant Dij: x 2
y z Dij x 2
y z CDij

Steady-state with  2Ci  2Ci  2Ci  2 xi  2 xi  2 xi

constant Dij, no  2  2 0 or  2  2 0
chemical reaction: x 2
y z x 2
y z

Steady-state, one-dimension,   D Ci    xi  N i

 ij   N i  0 or  ij
x 
D 
x  c
0
with chemical reaction: x  x 

36
General Conservation of Mass for a Mixture
Specie mass balance for dilute solutions
In most problems considered in this course, the solutions are dilute and
the fluid is imcompressible. Using molar flux based on fixed coordinates:

N i   Dij Ci  Ci v
Ci Ci
   N i N i       Dij Ci  Ci v   N i
t t
Ci
Rearrange:     Ci v      Dij Ci   N i
t

   Ci v   Ci   v  v Ci  v Ci
=0 for incompressible fluids ( = const.)
From continuity eqn 37
 Conservation of Mass for a Mixture
Specie mass balance for dilute incompressible solutions
Ci
   Ci v   v Ci   v Ci     Dij Ci   N i
t
Ci

  v Ci  Dij  Ci  N i
const. Dij 2

t
(constant diffusion coefficient)

Ni

Ni

Ni
38
 Boundary Conditions (Molar Basis)
1. Specified Surface Concentration
The concentration (CA) or mole fraction at a surface may
be specified to be constant (CA,s or xA,s) or a function of
space or time.

C A  C A,s @ x 0
x A  x A,s @ x 0
z = the position in the z-direction

This is:  the easiest for mathematics

 difficult to materialize/determine
39
 Boundary Conditions (Molar Basis)
2. Specified Mass Flux

The mass flux at or across the surface of a system may be

given/known.
C A
J   DAB
*
 J *A,s @z 0
z
A

x A
If C is constant: J A  CDAB  J *A,s @z 0
*

z

DAB = Binary diffusion coefficient

C = Total concentration

40
 Boundary Conditions (Molar Basis)
3. Impermeable Surface (No mass flux)
The mass flux at or across the surface of a system may be
negligible (analogous to insulated boundary in heat transfer).

C A
J   DAB
*
0 @z 0
z
A

If C is constant:
x A
0 @z 0
z

41
 Interface Boundary Condition
Discontinuous Concentrations at Interfaces
One phenomenon that makes mass transfer more
complex than heat transfer is the BC at the interface.
Heat transfer: Temperature is continous at the interface
(in case of perfect contact)

Mass transfer: Concentrations are

discontinous at the interface

Consider water pool which is exposed to air.

At the interface:
 Water mole fraction in the pool, xw,pool =1
 Water mol fraction in the air, xw,air  1
In general: BC at interface describes the
relationship between the concentrations on
either sides of the interface 42
 Boundary Conditions
4. Solid-Fluid Interface
Substance A is to lost to the surrounding from a solid
surface:
the concentration
of A in fluid stream

N A  hm  C A,s  C A,  @x 0

the mass flux of A at
the solid surface the concentration of
A at solid surface
mass transfer
coefficient

43
 Boundary Conditions
5. Chemical Reaction (catalytic surface reactions)
The rate of chemical reaction at the surface may be specified.
If A is consumed at the surface by a 1st order reaction:

N A  k R C A @x 0

6. Mass Transfer at the Gas-Liquid Interface

The gaseous substance A weakly soluble in the liquid B:
pA
xA  @x 0
H
H = Henry’s constant,
pA = the partial pressure of A 44
 Boundary Conditions
Evaporation of species A in the
liquid into gas B:
Raoult’s Law
pA
x A  vap @x 0
pA
pAvap  the vapor pressure of A, pA  the partial pressure of A

7. Mass Transfer at the Gas-Solid Interface

Gaseous substance A dissolved in solid B:

C A0  Sp A @ x 0

CA0 = the concentration of A in the solid at the interface

pA = the partial pressure of gas adjoining the interface
S = the solubility of A in the solid 45
 Boundary Conditions
8. Mass Transfer at the Liquid-Liquid Interface
Solute equilibrium at the interface between two immiscible
liquids:

C A,1   C A,2 @ x 0

CA,1 = the concentration of A in the liquid-1 at the interface

CA,2 = the concentration of A in the liquid-2 at the interface
 = the partition coefficient or solubility

The partition coefficient (also called distribution coefficient)

is used to describe solute equilibrium between a porous
medium and a fluid.
46
 Boundary Conditions
9. Mass Transfer at any Liquid-Liquid Interface
At the boundary between two immiscible liquids and gas-
liquid boundary, the fluxes in each fluid must be equal:

 1  N A,z
N A,z  2 @x 0

the flux of A in the the flux of A in the

liquid-1 at the liquid-2 at the
interface interface

47