MASS TRANSFER 1

CLB 20804

CHAPTER 1

MASS TRANSFER
BASIC PRINCIPLES AND APPLICATIONS
 Topic Outcomes
At the end of Chapter 1, you should:
• Define and explain the basic concept of mass transfer.
• Derive Fick’s Law equation.
• Calculate mass transfer rate based on unimolecular
diffusion and equimolar counterdiffusion.
• Explain the Inter phase mass transfer.
 What are in this chapter?

Introduction to
Basic Principles of
diffusion and
applications

Application to
unimolecular diffusion
Principles of Diffusion Fick’s Law
and equimolar
counterdiffusion
 Introduction

 Mass transfer refers to mass in transit due to a species

concentration gradient in a mixture.
 When a system contains two or more components whose
concentration vary from point to point , there is a natural
tendency for mass to be transferred.
 Minimizing the concentration differences within the system
and moving it towards equilibrium.
 Principles of Mass transfer

Mass transfer by ordinary molecular diffusion occurs because

of a concentration difference(driving force for transfer).

The mass transfer rate is proportional to the area normal to

the direction of mass transfer. Not to the volume. So, the rate
expressed as a flux.

Mass transfer stops when the concentration is uniform.

Mechanism of mass transfer involves both molecular diffusion
and convection.
 Molecular Diffusion
Net transport of molecules from a region of higher concentration to a
region of lower concentration by random molecular motion.

matter wants to "get away" from the other similar matter and go to a
place where there is open space.
 Molecular Diffusion

A B Liquids A and B are separated from each other.

Partition removed.

A goes from high concentration of A to low

A B concentration of A.
B goes from high concentration of B to low
concentration of B.

Molecules of A and B are uniformly distributed

everywhere in the vessel purely due to the
DIFFUSION.
 Example:
Molecular Diffusion

drop of liquid dye

Sprayed air freshener.

 Example of Mass Transfer
At the surface of the lung:

Air Blood
Oxygen

High oxygen concentration Low oxygen concentration

Low carbon dioxide concentration High carbon dioxide concentration

Carbon dioxide
 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.
 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.
 Properties of Mixtures

Chemical
Composition

Moles and Average Concentration

Mass and
Molecular Molecular
Mole Fractions
Weight Weight
Definitions
Definitions
Ci : Molar concentration  kmol/m  of species i.
3

i : Mass density (kg/m3) of species i.

Mi : Molecular weight (kg/kmol) of species i.

i  MiCi
J i* : Molar flux  kmol/s  m 2  of species i due to diffusion.
 Transport of i relative to molar average velocity (v*) of mixture.

N i : Absolute molar flux  kmol/s  m  of species i.

2

 Transport of i relative to a fixed reference frame.

ji : Mass flux kg/s  m  of species i due to diffusion.
2

 Transport of i relative to mass-average velocity (v) of mixture.

ni: Absolute mass flux  kg/s  m  of species i.
2

 Transport of i relative to a fixed reference frame.

xi : Mole fraction of species i  xi  Ci / C  .
mi : Mass fraction of species i  mi  i /   .
 Concentrations

 Molar concentration of species A:(liquids,solids) ,

(gases)
A
nA pA
cA   
MA V RT
 Where M A is molecular weight of species A.
 Mole fraction:


cA
x A  (liquids & solids)
c
cA
y A  ( gases )
c
For a gaseous mixture that obeys the ideal gas law,
mole fraction, y A can be written in terms of
pressures
p A RT p A
yA  
For gases, P RT P
Dalton’s
law
 General Fick’s Law Equation of diffusion
The basic empirical relation to estimate the rate of molecular
diffussion:
Fick’s Law

Molar Flux
dc A
Units -
mol/(s.m2)
J *
Az   DAB
dz
Diffusivity
(constant) J A z is the molar flux of A by ordinary molecular
Units -cm2/s diffusion relative to the molar average velocity of the
mixture in positive z direction, D AB is the mutual
diffusion coefficient of A in B, and dc A/dz is the
concentration gradient of A, which is
negative in the direction of ordinary molecular diffusion.

dy A
alternative form
J A  CDAB
dz
 Check your understanding-Theory of diffusion

Think of the last time that you washed the dishes. You placed the first
greasy plate into the water and the dishwater got a thin film of oil on the
top of it. Assume that there is no oil at the top of the sink yet. Find the
diffusion flux, J of oil droplets through the water to the top surface. The
sink is 18 cm deep, and the concentration of oil on the plate is 0.1
mol/cm3. Given the diffusivity is 7x10-7 cm2/s.

Given : D = 7x10-7 cm2/s.

Find : Calculate the flux.

6.1-1-Geankoplis(413)
Check your understanding-Theory of diffusion

dC = conc. at the top of the sink – conc. of oil on the plate.

The concentration at the top of the sink = 0

The concentration of oil on the plate = 0.1 mol/cm3.
dC = 0 – 0.1 = -0.1 mol/cm3

dx = the depth of the sink = 18 cm

J = 3.89 x 10-9 mol / (cm2.s)

 1.4 Diffusion Through Moving Bulk Fluid
Consider a bulk fluid of binary mixture A and B moving in the z-direction
as shown, with an average bulk fluid velocity V m/s, as shown in the Figure
below:

Concentration of A at any point in

the mixture = CA (kg-mole/m3)

Movement of A is now due to 2 contributions:

Molecular diffusion fluxes : ………(1)

Fluxes resulting from bulk flow= CAV (kg-mole/m3. m/s)

1.4.1 Diffusion Through Moving
Bulk Fluid
Molar flux of A :
N A  J A  C AV ………(2)

Similarly for comp. B:

………(3)
NB  J B  CBV
Total molar flux of A and B:

N A  NB  N ………(4)

Also, N = C V
………(5)
Where, C = total molar concentration
V= average molar velocity(m/s)
Substitute eqn (4) into eqn (5) :

N A  NB
V  ………(6)
C
1.4.1 Diffusion Through Moving
Bulk Fluid
Substitute eqn (1) & (6) into eqn (2) for comp. A:
• In term mole fraction:
dyA
N A  CDAB  yA( NA  NB )
dz

• In term concentration

………(7)

NA – Mass Transfer Relative to a fixed position

J*Az –Mass Transfer Relative to a mass or molar average velocity
 1.5 Steady-State Equimolar Counter-
Diffusion
 For binary mixture A and B,
 When gas system is closed and are connected by straight tube, and at
constant pressure and temperature.
 Molar fluxes A and B are equal, but opposite in direction
 Total pressure is constant throughout.

N  N A  NB  0 (1)

 Thus, diffussion flux are also equal but opposite in direction

Diffusivity, DAB = DBA

1.5 Steady-State Equimolar Counter-
Diffusion
Mass transfer in the connecting tube is equimolar counter
diffusion by molecular
1.5.1 Steady-State Equimolar Counter-
Diffusion
 Refer to eqn diffusion through moving bulk fluid:

 in term mole fraction

0
dyA
N A  cDAB  yA( NA  NB )
dz
dy
N  JA  cD AB
A
A
dz
 Integrated at z= z1, cA= cA1 and at z= z2, cA= cA2 to:
y
A2 dy A
J  cDAB 
A y dz
A1
 after simplify and rearrangement, the equation becomes :

DAB  
J  C  C
A ( z  z )  A1 A2 
2 1
1.5.2 Steady-State Equimolar Counter-
Diffusion of Ideal Gas Mixture:
 Consider 2-component gas mixture (A and B)
 Ideal Gas Law:

Pv  nRT
P = Total pressure
n = Total moles of gas

Component-A:

Where;
PAV  nART
pA = partial pressure of A
nA = moles of A
1.5.2 Steady-State Equimolar Counter-
Diffusion of Ideal Gas Mixture:

Concentration of A:
n   pA 
CA   A    
 V   RT  ………(1)

 Differentiating with respect to distance z

 dC A   dp A  1  ………(2)
     
 dz   dz  RT 

 Replacing into the original Fick's Law

D AB Dp A
JA   ………(3)
RT dz
Integrated Eqn(3) over a diffusional path from z2 to z1 & pA1 to PA2
D 
z2 PA2
J A.  dz   AB   dp A ………(4)
z1  RT  pA1
 1.5.2 Steady-State Equimolar Counter-
Diffusion of Ideal Gas Mixture:
Rearrange equation:
Diffusion flux for components A

JA 
DAB
 p A1  p A2  ………(5)
RT ( z 2  z1)

Diffusion flux for component-B

DAB ( pB1  p B 2 )
JB 
RT ( z 2  z1 )

where :
pA1 = partial pressure of A at point 1
pA2 = partial pressure of A at point 2:
 Steady-State Equimolar Counter-
Diffusion

In terms of concentration

DAB  
J  C C 
A ( z 2  z1)  A1 A2 

Or, In terms of partial pressure

D AB
JA   p A1  p A2 
RT ( z 2  z1)
Check your understanding
Ammonia gas (A) diffusing through a uniform tube 0.10 m long
containing N2 gas (B) at 1.0132x105 Pa pressure and 298 K. At point 1,
pA1=1.013x104 Pa and point pA2= 0.507x104 Pa. The diffusivity DAB =
0.230 x 10-4 m2/s. R = 8314 m3.Pa/kg-mole.K

(a) Calculate the diffusion flux JA at steady-state.

(b) Repeat for calculate the flux JB.

Given:
Total pressure PT = 1.0132 x 105 Pa
(constant)
Temperature T = 298 K
DAB = 0.230 x 10-4 m2/s
R = 8314 m3.Pa/kg-mole.K
At point 1, pA1 = 1.013 x 104 Pa
At point 2, pA2 = 0.507 x 104 Pa
Diffusion path = ( z2 - z1 ) = 0.1 m
Solution:
(a) Calculate the diffusion flux JA at steady-state.
DAB ( p A1  p A2 )
JA 
RT ( z 2  z1 )

Component-A is diffusing from Point 1 to Point 2, as its partial

pressure is higher at point 1.
(b) Calculate the diffussion flux JB.
 Use the Dalton's Law of partial pressures to determine the partial pressures
of component-B at points 1 and 2:

PT = pA + pB
At point 1:
pB1 = PT - pA1
PB1 = 1.0132 x 105 - 1.013 x 104 = 91,190 Pa
At point 2:
pB2 = PT - pA2
PB2 = 1.0132 x 105 - 0.507 x 104 = 96,250 Pa

Component-B is diffusing in the opposite direction to component-A:

from Point 2 to Point 1, as the partial pressure for B at point 2 is higher.
Calculate the flux of B in A using:

D AB ( p B1  p B 2 )
JB 
RT ( z 2  z1 )

Flux for component-B is the same as the flux for component-A, but
with a negative sign, indicating that it is in the opposite direction.
1.5.2 Steady-State Equimolar Counter-Diffusion of
Ideal Gas Mixture:

Rate of Diffusion= (molar flux) x (Surface area)

= JA x S

Where ;
Rate of Diffusion(unit: kmole/s)
JA= Diffusion flux of component A (kmole/m2 .s)
S= Surface area(unit m2 )
 1.6 Steady-State One component
Diffusions
 Opposite of equimolar counterdiffusion.
 One component diffuses, while the other remains stagnant
(nonmoving).

Fig 1.6

 Fig 1.6, point 0 is saturated with component A.

 while a stream of pure B flows past the end of the tube removing any A that
has reached point z.
 In this situation, the concentration gradient along the tube is exponential
 1.6 Steady-State One component
Diffusions
Example:
Diffusion of Components liquid benzene (A) through stagnant (nonmoving)
component air (B).

Evaporation of a pure (A) at the bottom of a narrow

tube.
Where a large amount of nondiffussing air (B) is
passed over the top.
Benzene vapor (A) diffuses through the air (B) in the
tube.
Point 1 (Boundary at the liquid surface) ~impermeable
to air (since air is insoluble in benzene liquid).
Hence, air (B) cannot diffuse into or away from the
surface.
Point 2~ partial pressure PA2=0(since a large volume of
air is passing by. Component B cannot diffuse,
NB=0
1.6 Steady-State One component Diffusions
Refer to equation diffusion through moving bulk fluid
dyA 0
N A  CDAB  yA( NA  NB )
dz
 Equation simplifies to

NA  CDAB
dyA
 yA( NA) ………(1)
dz
Rearrange eqn (1) to a fick’s law form
: dyA
N A  yA( NA)  CDAB ………(2)
dz
CD AB dy A
NA  
1  y A dz
1.6 Steady-State One component Diffusions
 At quasi steady state condition, rearange eqn becomes in integral form;
z2 CDAB yA 2 dy A
z1
dz  
NA 
yA1 1 yA
………(3)

 Upon integration yields Integration rules

CD 1 y 
N  ln  AB A2

A z  z 1 y
2 1
A1 
 ………(4)
 Log mean (LM) of (1-yA) at the two ends of the stagnants layer :

y A2  y A1 ………(5)
1  y A LM 
In1  y A2  /(1  y A1 )
 1  y A LM 
In1  y A  /(1  y Ai )
y Ai  y A
1  y A LM 
 Rearrange eqn (5) In1  y A  /(1  y Ai )
1  y A2  y A1  y A2
In 
(1  y A1 ) 1  y A LM
 Subsitute eqn (6)into eqn (4),

Finally:
the rate of diffusion is given by (in mole fraction terms)

CDAB y A1  y A2
NA 
z 2  z1 (1  y A ) LM
1.6.2 Steady-State One component Diffusions

 General equation Diffusion through moving bulk fluid:

 dC A  C A
N A   DAB  ( N A  NB ) ………(1)
 dz  C

 Component B cannot diffuse, NB= 0

 dC A  C A
N A   DAB  ( N A  0) ………(2)
 dz  C

using the Ideal Gas equation,

 P 
C   ………(3.1)
 RT 
 pA 
CA   
 RT  ………(3.2)
Divide eqn (3.2) with eqn (3.1);

CA

pA ………(4)
C P

 Differentiate eqn (3.2) with respect to distance z,

dC A  1  dp A 
   ………(5)
dz  RT  dz 

 Subsitute eqn (4) and (5) into eqn (2)

 dC  P
N A   DAB  A   A N A
 dz  P
re-arrange:
 p  D   dp A 
N A 1  A    AB  ………(6)
 P   RT   dz 
 Integrating Eqn (6) from point 1 to point 2: the partial pressure of
A changes from pA1 to pA2 :

 D AB 
z2 pA2
dp A
NA  dz     ………(7)
z1  RT  pA1 1   p 
 A P
  Integration rules

 Upon integration
 Log mean (LM) of (P-PA) at the two ends of the stagnants
layer :

P  PA LM  P  P PA1( PPPA2 ) ………(9)

P  PA LM  InPA2 PA2  /( PA1  PA1 )
InP  PA2  /( P  PA1 )
PA1  PA2
 P  PA LM 
InP  PA2  /( P  PA1 )
Rearange eqn (5)

In
P  PA2   PA1  PA2 ………(10)
( P  p A1 ) P  PA LM

Subsitute eqn (6)into eqn (4),

Finally: Rate of diffusion is given by (in partial pressure terms)

DAB P ( PA1  p A2 )
NA 
RT ( z2  z1 ) ( P  PA),LM
 Check your understanding
An open beaker, 6 cm in height, is filled with liquid benzene at 25°C to
within 0.5 cm of the top. A gentle breeze of dry air at 25°C and 1 atm is
blown by a fan across the mouth of the beaker so that evaporated
benzene is carried away by convection after it transfers through a
stagnant air layer in the beaker. The vapor pressure of benzene at 25°C
is 0.131 atm. The mutual diffusion coefficient for benzene in air at 25°C
and 1 atm is 0.0905 cm2/s. Determine the initial rate of evaporation of
benzene as a molar flux in mol/cm2.s

Evaporation of Benzene from a

beaker
 Solution:
Let A = benzene, B = air.

Take Zl = 0.
Then Z2 - Zl = ΔZ = 0.5 cm.

One component equation:

DAB P ( PA1  p A2 )
NA 
RT ( z2  z1 ) ( P  PA),LM

Log mean (LM) of (P-PA) at the two ends of the stagnants layer :

PA1  PA 2
P  PA LM 
InP  PA 2  /( P  PA1 )

P  PA LM 
0.131
 0.933
In1  0  /(1  0.131)
Then
0.0905 0.131 mol
NA   1.04 x10 6
0.5(298)(82.06) 0.933 cm 2 .s
1.7 Diffusion between phases - Phase
Equilibrium
 When two immiscible phases are in contact:
 Example. gas-liquid, two immiscible liquids, it is possible for
diffusing molecules to pass from one phase to the other across
the interphase boundary.
 When diffusion between two phases occurs, there are two
factors to take into account;

• Equilibrium relationships between the two phases

1

• rate at which the diffusion takes place

2
1.7 Diffusion between phases - Phase
Equilibrium

Fig 1.7

Referring to Fig 1.7:

 If a component, A is passing between phases 1 & 2, there will ultimately be a
dynamic equilibrium established where the rate of diffusion of A is the same in
both directions.
 Depending on the type of system (liquid – vapour, liquid – liquid etc.), the
equilibrium concentration may often be expressed by simple relationships.
1.7 Diffusion between phases - Phase
Equilibrium
2 simple relationships are :
 Distribution Coefficients

YA = KXA 1.6

Where
: XA = concentration of the component A in Phase 1

YA = concentration of the component A in Phase

2

K = constant
1.7 Diffusion between phases - Phase
Equilibrium
 Henry's Law

 Henry's law is a special case of the distribution coefficient for gas-

liquid systems.
 In the case of systems where one of the phases is a gas or vapour it
is common to express the concentration in the gas phase terms of
partial pressure.

Thus Henry's Law states that

PA = HCA

Whe P = Partial pressure of A in the gas phase

re: A
C = Concentration of A in the liquid phase
A
H = constant - called Henry's law constant
 1.8 Rate of diffusion between phases -
Mass Transfer
The theory discussed so far enables us to calculate the rates of
diffusion within a single phase and to calculate the concentrations
of a component in two phases when the system is in a state of
equilibrium.

However, many practical problems concern the rate of diffusion

between two phases when the two phases are not in equilibrium.

The rate of mass transfer between two phases is dependant on a

number of factors including:
1. The diffusivity of the diffusing component in the two
phases
2. How far the system is from equilibrium
3. The resistance to transfer across the interface between the
two phases
 1.8 Rate of diffusion between phases -
Mass Transfer
Mass Transfer Equation
Rate of mass transfer is directly proportional to the driving force for
transfer, and the area available for the transfer process to take place,
that is:
Transfer rate ∝ transfer area × driving force
The proportional coefficient in this equation is called the mass
transfer
coefficient, so that: N = kA ΔC
A A ×
Transfer rate = mass-transfer coefficient
transfer area × driving force

Wher NA = mass transfer rate of A across the

e: phase boundary
K = mass transfer coefficient
C = concentration driving force
 1.8 Interphase mass transfer
Two-Film Theory of Mass Transfer
►In order to illustrate the concept of
interphase mass transfer let’s consider
the process of transport of a volatile
chemical across the air/water
interphase.

Gas molecules must diffuse from the

main body of the gas phase to the
gas-liquid interface, then cross this
interface into the liquid side, and
finally diffuses from the interface into
the main body of the liquid.
 1.9 Concentration driving force
The concentration driving force is a measure of how far the system
is from equilibrium and may be developed with reference to the
diagram below. (Fig 1.9)

(Fig 1.9)

Consider a component, such as oxygen, diffusing from air to water. Assume the
system is at steady state but not at equilibrium.

 PA = partial pressure of oxygen in the air and CA is the concentration of

oxygen in the water.
 CA* = concentration of oxygen in water that will be in equilibrium with PA
 PA* = partial pressure of oxygen in air that will be in equilibrium with CA
 1.9 Concentration driving force

 The rate of oxygen mass transfer between air and water may be
expressed in two ways.
 One based on partial pressure of oxygen in air and one based on the
concentration of oxygen in water.

NA = KG (PA – P*A)

NA = KL (C*A – CA)

Wher PA – = partial pressure driving force

e: PA*
CA – = concentration driving force
CA*
KL = mass transfer coefficient based on the liquid phase.

KG = mass transfer coefficient based on the gas phase.

The approriate equilibrium value PA* or CA* may be calculated using Henry's law
Gas-Liquid Equilibrium Partitioning Curve
PA

PA = H’’ C*A
PA

PA,i = H CA,i
PA* = H CA
PA,i
PA = H CA*

P*A = H’ CA
P* A

CA CA,i C*A
CA
What have you learn from this
Chapter?