KS Rajmohan Diffusion Module 1 Jan 2016 Lecture1 Lecture10

Mass transfer I
KS RAJMOHAN
M.Tech (NIT Jamshedpur), PhD (IIT Madras)
Assistant Professor (Senior Scale)
Department of Chemical Engineering
II Floor , Energy house, UPES Dehradun
ksrajmohan@ddn.upes.ac.in
Mobile: 09994646610
08755276667
CHEG-212 MTO-I by KS Rajmohan

Reference Books
Treybal, R.E., ” Mass Transfer Operations “, McGraw-Hill Kogakusha, 1980.

J. D. Seader, Ernest J. Henley, D. Keith Roper, “Separation Process Principles”, 3rd
Edition, John Wiley & Sons, Inc.
Mccabe, W.L., Smith, J.C., and Harriot, P., ” Unit Operations in Chemical Engineering
“, McGraw-Hill Edn, 1993.
References
Coulson, J.M., Richardson, J.F., ” Chemical Engineering “, Pergamon Press, 1977.
Foust, A.S.Wenzel, L.A., Clump, C.W., Naus, L., and Anderson, L.B., ” Principles of Unit
Operations “, Second Edition, Wiley, 1980.
Sherwood, T.K., Pigford, R.L., and Wilke, C.R., ” Mass Transfer “, McGraw-Hill, 1976.
Roman Zarzytci, Andrzai Chacuk, ” Absorption: Fundamentals and Application “, Pergamon
Press, 1993.
Skelland, A.H.P., ” Diffusional Mass Transfer “, Krieger, Malabar FL (1985).
Strigle (jr), R.F., ” Packed Tower Design and Applications “, Second Edition, Gulf Publishing
Company, USA., 1994.
Strumila, C.Kudra, T., ” Drying Principles: Applications and Design “, Gordan and Breath
Science Publishers, U.K., 1986.

Syllabus for Mass Transfer Operations-I
Diffusion
• Molecular and eddy diffusion in gases and liquids,
• Steady state diffusion under stagnant and laminar flow conditions
• Diffusivity measurement and prediction Multicomponent diffusion,
• diffusion in solids and its applications.
Mass Transfer Coefficients
Concept of mass transfer coefficients, mass transfer under laminar and turbulent flow past solids, boundary
layers, mass transfer at fluids surfaces correlation of mass transfer coefficients, JD,HTU,and NTU concepts,
theories of mass transfer and their applications, interphase mass transfer and over all mass transfer coefficients
in binary and multicomponent systems, application to gas-liquid and liquid-liquid systems.
Gas Absorption
Gas Dispersed, Sparged vessels (Bubble Columns), Mechanical agitated equipments, Tray towers, General
characteristics, Sieve design for absorption and distillation, Different types of Tray Efficiencies, Liquid Dispersed
Venturi Scrubbers, Wetted-Wall Towers, Packed Towers, Counter current flow of Liquid & Gas through packing,
Mass transfer coefficients for packed towers, Tray vs Packed towers
DISTILLATION
Fields of applications, VLE for miscible liquids, immiscible liquids, steam distillation, Positive and negative
deviations from ideality, enthalpy-concentration diagrams
flash vaporization and differential distillation for binary and multi component mixtures.
Continuous rectification-binary systems, multistage tray towers Method of Mc Cabe and Thiele, enriching
section, exhausting section Feed introduction, total reflux, minimum and optimum reflux ratios Use of steam,
condensers, partial condensers Cold reflux, multiple feeds , tray efficiencies

Course plan

Learning objectives (Module 1)
Learners will be able to
 Explain the common causes of difffusion
 State Fick ‘s First law of diffusion
 Distinguish between molecular and eddy diffusion
 Explain the effect of temperature and pressure on diffusivity of
gases
 Define the terms J-flux and N-flux
 Explain when equimolar counter diffusion occurs
 Write Wilke-Chang equation and explain its significance
 Define Knudsen diffusivity and state its application
 Derive expressions for steady state molecular diffusion of gases:
 Equimolar counter diffusion of A and B
 A diffusing in Stagnant B
 Derive an expression for determining diffusivity of a vapour in air
using Arnold diffusion cell
 Explain Hiebie’s penetration theory
 Concept of Two resistance theory
 Derive an expression between individual and overall mass transfer
coefficients (MTC)
 Numerical on diffusivity, flux, solvent loss, MTC
Chemical plant
Purification Chemical Purification
reactor
Concentration final
-------------------------- = high , Final cost is high
Concentration initial
When a substance is available in high concentration, it is cost is low.
Example: H2SO4 is cheap ,
whereas
When a substance is available in low concentration , its cost is high
Example: uranium
Separation methods:
Mechanical operation:
Filtration of solids
Screening
Mass transfer operations

Mass transfer operations
Examples of industrial MTO:

Remediation of polluted air,water and soil: Separation of CO2 from flue gases:
Absorption
Energy generation
Purification and separation: Ethanol water system Distillation
Toluene water mixture:Extraction (Using benzene )
Extract perfume from plants
Evaporate sea water to produce salt
G-L-S
G-G G-L G-S L-L L-S S-S

Practically
not Absorption Drying Crystallization Very slow
realistic Adsorption Extraction Leaching diffusion
Distillation process
c

General Considerations
• Mass transfer refers to mass in transit due to a species concentration gradient

in a mixture.
 Must have a mixture of two or more species for mass transfer to occur.
 The species concentration gradient is the driving potential for transfer.
 Mass transfer by diffusion is analogous to heat transfer by conduction.
• Physical Origins of Diffusion:

 Transfer is due to random molecular motion.
 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.
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  of species i due to diffusion.
2
 Transport of i relative to molar average velocity (v*) of mixture.
Ni : Absolute molar flux  kmol/s  m2  of species i.

 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 
2
of species i.
 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 /   .

Property Relations
• Mixture Concentration:
C   Ci   xi  1
i i
• Mixture Density:
   i   mi  1
i i
• Mixture of Ideal Gases:

p
Ci  i
iT
pi
i 
RiT
p   pi
i
Ci pi
xi  
C p

Molecular Mass Transfer
 Molecular diffusion
 Mass transfer law components:
 Molecular concentration:
A
nA p A
cA   
M A V RT
 Mole fraction:
cA cA
xA  (liquids,solids) ,
yA  (gases)
c c
p A RT p A
For gases,y A  
P RT P
n n
 Velocity:  v  i i i vi
mass average velocity, v  i 1
 i 1
n

 i
i 1
n
c v i i
molar average velocity,V  i 1
c
velocity of a particular species relative to mass/molar

average is the diffusion velocity.

mol

Mass Transfer
Convective
Molecular Diffusion
Mass Transfer
Gases Liquid Solid

DIFFUSION
When drops of dye are added to a beaker of water, the

drops are areas of high concentration of dye molecules.
They will eventually be evenly distributed among the
water molecules, and although all the molecules
continue to be in motion, no further change will be
observed.

All molecules are in constant motion unless at
absolute zero.
The motion is random, with molecules moving
in straight lines until they encounter other
molecules.
The net result of this process is diffusion: the
movement of a substance from an area where it
is in high concentration to an area where it is in
low concentration.

Water and small, non-charged molecules have no difficulty crossing the lipid
portion of the membrane. Ions and charged molecules cannot cross easily, nor
can large molecules. It is important that many types of substances be able to
enter or leave cells. There is a variety of mechanisms by which this occurs, some
requiring energy and some utilizing carrier proteins.
Lipid - Organic compound that is insoluble in water; notably fats, oils, and
steroids.
Ions - Atom or group of atoms carrying a positive or negative charge.
Energy - Capacity to do work and bring about change; occurs in a variety of
forms.
Carrier Protein - Protein molecule that combines with a substance and
transports it through the plasma membrane.

Molecules that readily cross the plasma membrane enter or
leave cells by diffusion. Diffusion is the result of random
molecular motion. Molecules move in straight lines until they
encounter obstacles. There are more obstacles where
molecules are highly concentrated, so a substance will tend
to move from an area of high to an area of low concentration.

Gas exchange in the lungs occurs by diffusion.
Carbon dioxide (CO2) will follow its concentration
gradient into the alveolus, oxygen (O2) will follow
its concentration gradient into the capillary.
Lungs - Paired, cone-shaped organs within the
thoracic cavity, functioning in internal respiration
and containing moist surfaces for gas exchange.
Diffusion - Movement of molecules from a
region of higher concentration to a region of
lower concentration.
Alveolus - (pl, alveoli) - Air sac of a lung.
Capillary - Microscopic vessel connecting
arterioles to venules and through the thin walls of
which substances either exit or enter blood.

Advection and Diffusion….
Transport processes in the environment may be

divided into two categories: advection and diffusion.
Advection refers to transport with the mean fluid
flow.
For example, if the wind is blowing toward the east,
advection will carry any pollutants present in the
atmosphere toward the east.
Similarly, if a bag of dye is emptied into the center
of a river, advection will carry the resulting spot of
dye downstream. In contrast, diffusion refers to the
transport of compounds through the action
of random motions.
Advection and Diffusion….
Diffusion works to eliminate sharp discontinuities in

concentration and results in smoother, flatter concentration
profiles.
Advective and diffusive processes can usually be
considered independently.
In the example of a spot of dye in a river, while advection
moves the center of mass of the dye downstream, diffusion
spreads out the concentrated spot of dye to a larger, less
concentrated region.

DIFFUSION VS. EFFUSION?
Effusion is the process in which a

gas escapes through a small hole.
This occurs if the diameter of the
hole is considerably smaller than
the mean free path of the
molecules.
According to Graham's law, the rate at which gases effuse

(i.e., how many molecules pass through the hole per
second) is dependent on their molecular weight. Gases
with a higher molecular weight effuse more slowly than
gases with a lower molecular weight;

Rate of effusion :Graham Law
Thomas Graham (1805–1869), a Scottish chemist, found

experimentally that the rate of effusion of a gas is inversely
proportional to the square root of the mass of its particles. In other
words, the relative rates of effusion of two gases at the same
temperature and pressure are given by the inverse ratio of the square
roots of the masses of the gas particles.
The equation is given by where and represent the molar masses of
the gases. This equation is known as Graham's law of effusion.

Transfer Processes
 Three fundamental transfer processes:

i) Momentum transfer
ii) Heat transfer
iii) Mass transfer

 Mass transfer may occur in a gas mixture,
a liquid solution or solid.
 Mass transfer occurs whenever there is a
gradient in the concentration of a
species.
 The basic mechanisms are the same
whether the phase is a gas, liquid, or solid.

Definition of Concentration
i) Number of molecules of each species

present per unit volume (molecules/m3)
ii) Molar concentration of species i =
Number of moles of i per unit volume
(kmol/m3)
iii) Mass concentration = Mass of i per unit
volume (kg/m3)

Diffusion phenomena
T,P,F,K
 Fick’s law: linear relation between the rate of
diffusion of chemical species and the
concentration gradient of that species.
 Thermal diffusion: Diffusion due to a temperature
gradient. Usually negligible unless the
temperature gradient is very large.
 Pressure diffusion: Diffusion due to a pressure
gradient. Usually negligible unless the pressure
gradient is very large.

 Forced diffusion: Diffusion due to
external force field acting on a molecule.
Forced diffusion occurs when an
electrical field is imposed on an
electrolyte ( for example, in charging an
automobile battery)
 Knudsen diffusion: Diffusion phenomena
occur in porous solids.

 Whenever there is concentration difference in a medium,
nature tends to equalize
things by forcing a flow
from the high to the low
concentration region.
Before After
 The molecular transport process of mass is characterized

by the general equation:
Rate of transfer process = driving force

resistance
Example of Mass Transfer Processes
 Consider a tank that is divided into two equal parts by a
partition.
 Initially, the left half of the tank contains nitrogen N2 gas while
the right half contains O2 at the same temperature and pressure.
 When the partition is removed the N2 molecules will start
diffusing into the air while the O2 molecules diffuse into the N2.
 If we wait long enough, we will have a homogeneous mixture of
N2 and O2 in the tank.

 Liquid in open pail of water evaporates into air
because of the difference in concentration of water
vapor at the water surface and the surrounding air.
 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.

 Molecular diffusion or molecular transport can be defined as the
transfer or movement of individual molecules through a fluid by mean
of the random, individual movements of the molecules.
(2) A
B
B B
B B B
B
B Figure 3: Schematic diagram of molecular diffusion process
B B
(1) A
 If there are greater number of A molecules near point (1) than at (2),
then since molecules diffuse randomly in both direction, more A
molecules will diffuse from (1) to (2) than from (2) to (1).
 The net diffusion of A is from high to low concentration regions.

Molecular Diffusion Equation
dcA
J *
AZ   DAB
dz
*
JA is the molar flux of component A in the z
mol A/s.m2.
direction in kg
is the molecular diffusivity of the molecule A in B in m2/s

DAB
cA is the concentration of A in kg mol/m3.
z is the distance of diffusion in m

Fick’s first law of diffusion
 Fick proposed a relationship of diffusion of matter similar to Fourier’s
equation for heat. He proposed that the flux of particles is proportional to
the gradient in concentration of particles. In one dimension this is written:
dc
j  D
dx
 The flux density j of particles has units e.g. #/(cm2s) or mol/(cm2s)
 The concentration is given in e.g. #/cm3 or mol/cm3
 The diffusion coefficient (or diffusion constant) then has units cm2/s
 The minus sign states that the flux goes down the concentration gradient.
The negative of the concentration gradient may be taken as the driving
force.

Comments on Ficks Law
 Fick’s first law is a phenomenological – or empirical – expression; It

describes a flux in terms of a concentration gradient and a
proportionality coefficient – the diffusion coefficient, or diffusivity.
 However, Fick’s first law applies strictly only to neutral non-interacting
particles. Examples comprise dilute solutions of interstitial atoms, e.g.
atomic H in metals.
 For other situations, the coefficient in Fick’s first law is not a constant.
 D in Fick’s first law has not been given any physical meaning upto now –
it remains a phenomenological coefficient. In the next model, we will
give it more content.

Diffusion
Diffusion - Mass transport by atomic motion.
Diffusion is a consequence of the constant
thermal motion of atoms, molecules and
particles that results in material moving from
areas of high to low concentration.
Mechanisms
 Brownian motion is the seemingly random
movement of particles suspended in a liquid or
gas.
 Solids – vacancy diffusion or interstitial
diffusion.
4
CHEG-212
4 MTO-I by KS Rajmohan
 Applications of Diffusion
 Activation Energy for Diffusion
 Mechanisms for Diffusion
 Rate of Diffusion (Fick’s First Law)
 Factors Affecting Diffusion
 Composition Profile (Fick’s Second Law)

 The two modes of mass transfer:
- Molecular diffusion
- Convective mass transfer

Diffusion
Diffusion results from random motions of two
types: the random motion of molecules in a fluid,
and the random eddies which arise in turbulent
flow.
Diffusion from the random molecular motion is
termed molecular diffusion; diffusion which
results from turbulent eddies is called turbulent
diffusion or eddy diffusion.
We will compare these two types of diffusion

below. First, however, we consider why diffusion
occurs.
Fick's Law
In this section, we will derive Fick's Law, the equation
which is used to calculate the diffusive flux density, by
analyzing the results of random motion of a
hypothetical box of molecules. The purpose of this
derivation is to provide a qualitative and intuitive
understanding of the reason that diffusion occurs, and
the derivation itself is useful only for that purpose. In
problems where it is necessary to actually calculate the
diffusive flux, we will normally start at the end of this
derivation---that is with the Fick's Law equation
(equation 40). (This derivation is based closely on one
presented in Mixing in Inland and Coastal Waters, H. B.
Fischer, E. J. List, J. Imberger, and N. H. Brooks,
Academic Press, New York, 1979.)
Molecular diffusion
The diffusion of molecules when the whole

bulk fluid is not moving but stationary.
Diffusion of molecules is due to a
concentration gradient.
The general Fick’s Law Equation for binary mixture of A and B
dxA
J *
AZ  cDAB
dz
c = total concentration of A and B [kgmol (A + B)/m3]
xA= mole fraction of A in the mixture of A and B

Example
A mixture of He and N2 gas is contained

in a pipe at 298 K and 1 atm total
pressure which is constant throughout.
At one end of the pipe at point 1 the
partial pressure pA1 of He is 0.6 atm and
at the other end 0.2 m pA2 = 0.2 atm.
Calculate the flux of He at steady state if
DAB of the He-N2 mixture is 0.687 x 10-4
m2/s.

Solution
 Since a total pressure P is constant, the c is constant, where c is
as follows for a gas according to the perfect gas law:
 Where n is kg mol A plus B, V is volume in m3, T is temperature

in K, R is 8314.3 m3.Pa/kg mol.K or R is 82.057 x 10-3 cm3.
atm/g. mol. K, and c is kg mol A plus B/m3.
 For steady state the flux J*Az in Eq.(6.1-3) is constant. Also DAB
for gas is constant. Rearranging Eq. (6.1-3) and integrating.
(6.1-11)
 Also, from the perfect gas law, pAV=nART, and
 Substituting Eq. (6.1-12) into (6.1-11),
(6.1-13)
 This is the final equation to use, which is in a form eqsily used for
gases. Partial pressures are pA1 = 0.6 atm = 0.6 x 1.01325 x 105
= 6.04 x 104 Pa and pA2 = 0.2 atm = 0.2 x 1.01325 x 105 = 2.027
x 104 Pa. Then, using SI units,

 If pressures in atm are used with SI unit,
 Other driving forces (besides concentration

differences) for diffusion also occur because
of temperature, pressure, electrical potential,
and other gradients.

Convection Mass Transfer
 When a fluid flowing outside a solid surface in forced convection motion,
rate of convective mass transfer is given by:
N A  kc (cL1  cLi )
kc - mass transfer coefficient (m/s)
cL1 - bulk fluid conc.
cLi - conc of fluid near the solid surface
 Kc depend on:
1. system geometry
2. Fluid properties
3. Flow velocity

Diffusion
 How do we quantify the rate of diffusion?
moles (or mass) diffusing mol kg

J  Flux   or 2
surface areatime 2
cm s m s
• Measured empirically
– Make thin film (membrane) of known surface area
– Impose concentration gradient
– Measure how fast atoms or molecules diffuse through the membrane
M=
M 1 dM mass J  slope
J  diffused
At A dt
time
5
CHEG-212
Steady-state diffusion across a thin plate
Rate of diffusion is independent of time; the diffusion flux does
not change with time.
The concentration profile shows the concentration (C) vs the position within
the solid (x); the slope at a particular point is the concentration gradient.
Steady-State Diffusion
dC
Flux proportional to concentration gradient =
dx
C1 C1 Fick’s first law of diffusion
dC
C2 C2 J  D
dx
x1 x2
x
D  diffusion coefficient
dC C C2  C1
if linear  
dx x x2  x1
5
CHEG-212
Example 1: Chemical Protective Clothing (CPC)
 Methylene chloride is a common ingredient of paint

removers. Besides being an irritant, it also may be
absorbed through skin. When using this paint
remover, protective gloves are worn.
 If butyl rubber gloves (0.04 cm thick) are used, what is
the diffusive flux of methylene chloride through a
glove?
 Data:
 diffusion coefficient for butyl rubber:
D = 110 x10-8 cm2/s
 surface concentrations:
C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
5
CHEG-212
Example 1 (cont).
• Solution – assuming linear conc. gradient
glove
C1 dC C2  C1
tb 
2 J -D  D
paint
6D dx x2  x1
skin
remover
C2 Data: D = 110 x 10-8 cm2/s
x1 x 2 C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 – x1 = 0.04 cm
-8 2(0.02 g/cm3  0.44 g/cm3 ) g

J   (110 x 10 cm /s)  1.16 x 10-5
(0.04 cm) cm2s
1.15 x 10-4kg/m
2
5 .s
CHEG-212
CPC Example (cont.)
• Solution – assuming linear conc. gradient
glove Breakthrough time = tb
C1
2 Equation from online CPC
tb 
Case Study 5 at the Student
paint skin Companion Site for Callister &
remover 6D Rethwisch 8e (www.wiley.com/
college/callister)
C2
  x2  x1  0.04 cm
x1 x 2
D = 110 x 10-8 cm2/s
(0.04 cm)2
tb   240 s  4 min
-8 2
(6)(110 x 10 cm /s)
Time required for breakthrough ca. 4 min

6
0
Summary
Diffusion FASTER for... Diffusion SLOWER for...
• open crystal structures • close-packed structures
• materials w/secondary • materials w/covalent

bonding bonding
• smaller diffusing atoms • larger diffusing atoms
• lower density materials • higher density materials
6
1
E.R. Gilliliand: "Diffusion Coefficients in Gaseous Systems"
Industrial & Engeneering Chemistry , Volume 26 (1934) Page 681-685

Diffusion and Temperature
• Diffusion coefficient increases with increasing T.
 Qd 
D  Do exp 
 RT 
D = diffusion coefficient [m2/s]

Do = pre-exponential [m2/s]
Qd = activation energy [J/mol or eV/atom]
R = gas constant [8.314 J/mol-K]
T = absolute temperature [K]
Activation energy - energy required to produce the movement

of 1 mole of atoms by diffusion.
6
CHEG-212
Factors that influence diffusion
 The diffusing species, host material and temperature

influence the diffusion coefficient.
 For example, there is a significant difference in magnitude
between self-diffusion and carbon interdiffusion in α iron at
500 °C.
Example 2: At 300ºC the diffusion coefficient and
activation energy for Cu in Si are:
D(300ºC) = 7.8 x 10-11 m2/s
Qd = 41,500 J/mol
What is the diffusion coefficient at 350ºC?
Q
transform  d 
D ln D D  Doexp RT 
data
Temp = T 1/T
Qd  1  Qd  1 
lnD300  lnD0    and lnD350  lnD0   
R  T300  R  T350 
D350 Qd  1 1 
 lnD350  lnD300  ln    
D300 R  T 350 T 300 
6
CHEG-212
Example 2 (cont.)
 Qd  1 1 
D2  D1 exp   
 R  T2 T1 
T1 = 273 + 300 = 573 K

T2 = 273 + 350 = 623 K
11 2   41,500 J/mol  1 1 

D2  (7.8 x 10 m /s) exp   
 8.314 J/mol - K  623 K 573 K 
D2 = 15.7 x 10-11 m2/s
6
CHEG-212
Definition of the Mass Flux Density
We used the term mass flux (, with units of mass/time) earlier when we
calculated the rates at which mass was transported into and out of a
control volume in a mass balances.
Because mass balance calculations are always made with reference to a
specific control volume, it was clear that this value referred to the rate at
which mass was transported across the boundary of the control volume.
In our calculations of advective and diffusive fluxes, however, we will not
restrict ourselves to a specific, well-defined control volume.
Instead, we will calculate the flux density across an imaginary plane
oriented perpendicular to the direction of mass transfer.

Definition of the Mass Flux Density
The resulting mass flux density is defined as the rate of mass transferred
across the plane per unit time per unit area, with units of (mass)/. We will
use the symbol J to represent the flux density.
J represents the mass flux density, expressed as the rate per unit area at
which mass is transported across an imaginary plane. J has units of
[M]/[LT].The total mass flux across a boundary () can be calculated from
the flux density simply by multiplying J by the area of the boundary:
In the following sections, we will consider the flux density

which results from advection and from diffusion. The
symbol J will be used to represent the flux density in each
case, whether the flux is a result of advection, diffusion, or
a combination of both processes.

Calculation of the Advective Flux
The advective flux refers to the movement of a compound along with flowing
air or water. The advective flux density depends simply on concentration
and flow velocity.
The fluid velocity, v, is a vector quantity---it has both magnitude and
direction, and the flux J refers to the movement of pollutant mass in the
same direction as the fluid flow. In this course, we will generally define our
coordinate system so that the x-axis is oriented in the direction of fluid flow.
In this case, the flux J will reflect a flux in the x-direction, and we will
generally ignore the fact that J is really a vector.

Mixing Problem A sewage pipe from a wastewater treatment plant discharges 1.0 m s /
of effluent containing 5.0 mg/l of phosphorus compounds (reported as mg P/l) into a

river with an upstream flow rate of 25 m s and a phosphorus concentration of 0.010 mg
/
P/l (see Figure 2). What is the resulting concentration of phosphorus in the river
downstream of the sewage outflow, in units of mg/l?
Solution: To solve this problem, we will apply two mass balances to determine first the
downstream volumetric flow rate ( Qd/s ) and, second, the downstream phosphorus
concentration ( ). But first, we must select a control volume. To ensure that the input
and output fluxes cross the control volume boundaries, the control volume must cross
the river upstream and downstream of the sewage outlet and must cross the sewage pipe.
The selected control volume is shown in Figure 2 as a dotted line. We must assume that
the control volume extends down the river far enough that the sewage and the river
water become well-mixed before leaving the control volume. As long as that assumption
is met, it makes absolutely no difference to our analysis how far downstream the control
volume extends.
Before beginning our analysis, we should determine whether this is a steady-state or
non-steady-state problem, and whether the chemical reaction term will be nonzero.
Since the problem statement does not refer to time at all, and it seems reasonable to
assume that both the river and sewage have been flowing for some time and will
continue to flow, this is a steady-state problem. Sewage does participate in chemical and
biologicalMTO-I
CHEG-212 reactions.
by KSHowever,
Rajmohanwe are interested here in mixing---that is, in what
Example .. Calculation of the advective flux
density. Calculate the average flux density J of
phosphorus downstream of the sewage pipe of
example 2.1. The cross-sectional area of the river is 30
m.
Solution: In example 2.1, we found the following
conditions downstream of the spot where a sewage
pipe added effluent to a river: volumetric flow
rate and as phosphorus. The average river velocity is .
Using the definition of flux density (equation 32), we
find:

Problem
Gasoline-contaminated groundwater has been transported under a house
from a nearby gas station. Two meters below the dirt floor of the house's
basement, the concentration of hydrocarbon vapors in the airspace within
the soil is …. g/cm. Estimate the flux density of gasoline vapor transported
into the basement by molecular diffusion. The diffusion coefficient for
gasoline vapor in the air space within the soil is equal to …cm/s. Assume
that the basement is well-ventilated, so that the concentration of gasoline in
the basement is very small in comparison to the concentration in the soil.
assuming that the gradient

of concentration with height
is linear over the 2 m depth

The calculated flux density of can be used to calculate the
total mass flux of gasoline into the basement using
equation 31. If the basement floor has an area of 100 m, then
the total flux into the basement is

Diffusion
 How does diffusion occur?
 Why is diffusion an important part of processing?
 How can the rate of diffusion be predicted for some simple
cases?
 How does diffusion depend on structure and temperature?
7
CHEG-212
Applications of Diffusion
Diffusion in Solids, P.G. Shewmon , McGraw-Hill, New York (1963)

• Furnace for heat treating steel using carburization.
• Carburizing is the addition of carbon to the surface of low-
carbon steels at temperatures ranging from 1560°F to
1740°F.
• Hardening is achieved when a high carbon martensitic case
with good wear and fatigue resistance is superimposed on a
tough, low-carbon steel core.
http://www.americanmetaltreatinginc.com/carburizing.htm
Case Hardening
• Case hardening or surface hardening is
the process of hardening the surface of a
metal, often a low carbon steel, by diffusing
elements into the material's surface, forming
a thin layer of a harder alloy.
• Carbon atoms diffuse into the iron lattice
atoms at the surface.
• This is an example of interstitial diffusion.
• The C atoms make iron (steel) harder.
“Carbide band saw blade can cut

through case hardened materials.” 78
Thomson Learning™ is a trademark used herein under license.
©2003 Brooks/Cole, a division of Thomson Learning, Inc.
Schematic of the
microstructure of the Co-
Pt-Ta-Cr film after
annealing.
Most of the chromium
diffuses from the grains to
the grain boundaries after
the annealing process.
This helps improve the
magnetic properties of the
hard disk.
http://www.asylumresearch.com/Gallery/Materials/Materials.shtml

• Hot-dip galvanizing is a form of galvanization. It is
the process of coating iron, steel, or aluminum with a thin
zinc layer, by passing the metal through a molten bath of
zinc at a temperature of around 860 °F (460 °C).
• When exposed to the atmosphere, the pure zinc (Zn)
reacts with oxygen (O2) to form zinc oxide (ZnO), which
further reacts with carbon dioxide (CO2) to form zinc
carbonate (ZnCO3), a dull grey, fairly strong material.
• In many environments, the steel below the coating will
be protected from further corrosion.
•Galvanized steel is widely used in applications where A hot-dip galvanizing 'kettle' with fume hood
rust resistance is needed.
Galvanized steel and coils popular
for applications in industrial goods,
automobile components, precision
tubes, consumer durable and many
more.
Galvanized i-beams.

Thermal barrier coatings (TBC) with a ceramic topcoat are widely used for
protecting highly loaded gas turbine components against overheating.
For example, on internally cooled turbine blades the ceramic topcoat maintains a
high temperature difference between the outer surface and the underlying metallic
8 substrate.
CHEG-212
Doping by Diffusion
 Integrated circuits (ICs), found in
numerous electronic devices
have been fabricated using
doping techniques.
 The base material for these ICs
is silicon that has been “doped”
with other materials.
 More precisely, controlled
concentrations of impurities have
been diffused into specific
regions of the device to change
the properties (improve electrical
conductivity).

Processing Using Diffusion
• Doping silicon with phosphorus for n-type semiconductors:
• Process: 0.5 mm
1. Deposit P rich
layers on surface.
magnified image of a computer chip
silicon
2. Heat.
3. Result: Doped light regions: Si atoms
semiconductor
regions.
light regions: Al atoms

silicon
83
Interdiffusion
• Interdiffusion (impurity diffusion): In an alloy,
atoms tend to migrate from regions of high
concentration to regions of low concentration.
After some time
Initially
8
CHEG-212
Self-Diffusion
• Self-diffusion: In an elemental solid,
atoms also migrate.
specific atom movement After some time
C
C
A D
A
D
B
B
8
CHEG-212
Diffusion Mechanisms
 Atoms in solid materials are in constant motion, rapidly
changing positions.
 For an atom to move, 2 conditions must be met:
1. There must be an empty adjacent site, and
2. The atom must have sufficient (vibrational) energy to
break bonds with its neighboring atoms and then
cause lattice distortion during the displacement.
At a specific temperature, only a small fraction of the
atoms is capable of motion by diffusion. This fraction
increases with rising temperature.
 There are 2 dominant models for metallic diffusion:
1. Vacancy Diffusion
2. Interstitial Diffusion

Vacancy Diffusion
Vacancy Diffusion:
• atoms exchange with vacancies
• applies to substitutional impurity atoms
• rate depends on:
-- number of vacancies
-- activation energy to exchange.
increasing elapsed time

8
CHEG-212
Interstitial Diffusion
 Interstitial diffusion – smaller atoms (H,

C, O, N) can diffuse between atoms.
More rapid than vacancy diffusion due to more

8 mobile small atoms and more empty interstitial sites.
CHEG-212
Molecular Diffusion in Gases
 Equimolar Counterdiffussion in Gases

 For a binary gas mixture of A and B, the
diffusivity coefficient DAB=DBA

Example 6.2-1
Ammonia gas (A) is diffusing through a
uniform tube 0.10 m long containing N2
gas (B) at 1.0132 x 105 Pa pressure and
298 K. The diagram is similar to Fig. 6.2-
1. At point 1, pA1 = 1.013 x 104 Pa and
at point 2, pA2 = 0.507 x 104 Pa. The
diffusivity DAB = 0.230 x 10-4 m2/s.
(a) Calculate the flux J*A at steady state
(b) Repeat for J*B

Solution
 Equation (6.1-13) can be used, where P = 1.0132 x 105 Pa, z2-z1
= 0.10 m, and T = 298 K. Substituting into Eq. (6.1-13) for part
(a),
 Rewriting Eq. (6.1-13) for component B for part (b) and noting
that pB1 = P – pA1 = 1.01325 x 105 – 1.013 x 104 = 9.119 x 104 Pa
and pB2 = P – pA2 = 1.01325 x 105 – 0.507 x 104 = 9.625 x 104
Pa.
 The negative for J*B means the flux goes from point 2 to point 1.

Diffusion of Gases A and B
Plus Convection

For equimolar counterdiffussion, NA=-NB ,
then NA=J*A=-NB=-J*B
Example 6.2-2
Water in the bottom of a narrow metal tube is held at a
constant temperature of 293 K. The total pressure of air
(assumed dry) is 1.01325 x 105 Pa (1.0 atm) and the
temperature is 293 K (20 °C). Water evaporates and
diffuses through the air in the tube, and the diffusion
path z2-z1 is 0.1524 m (0.5 ft) long. The diagram is
similar to Fig. 6.2-2a. Calculate the rate of evaporation
at steady state in lb mol/h.ft2 and kg mol/s.m2. The
diffusivity of water vapor at 293 K and 1 am pressure is
0.250 x 10-4 m2/s. Assume that the system is
isothermal. Use SI and English units.

Solution
 The diffusivity is converted to ft2/h by using the conversion factor:
 From Appendix A.2 the vapor pressure of water at 20 °C is 17.54

mm, or pA1 = 17.54/760 = 0.0231 atm = 0.0231(1.01325 x 105) =
2.341 x 103 Pa, pA2 = 0 (pure air). Since the temperature is 20 °C
(68 °F), T = 460 + 68 °R = 293 K. From Appendix A.1, R = 0.730
ft3.atm/lb mol.°R . To calculate the value of pBM from Eq. (6.2-21)

 Since pB1 is close to pB2, the linear mean (pB1+pB2)/2
could be used and would be very close to pBM.
 Substituting into Eq. (6.2-22) with z2-z1 = 0.5 ft
(0.1524m),

Example 6.2-4
A sphere of naphthalene having a radius of 2.0

mm is suspended in a large volume of still air at
318 K and 1.101325 x 105 Pa (1 atm). The
diffusivity of the naphthalene at 318 K is 6.92 x
10-6 m2/s.
Calculate the rate of evaporation of
naphthalene from the surface.

Solution
 The flow diagram is similar to Fig. 6.2-3a. DAB = 6.92 x 10-6 m2/s,
pA1 = (0.555/760)(1.01325 x 105) = 74.0 Pa, pA2 = 0, r1 = 2/1000
m, R = 8314 m3.Pa/kg mol.K, pB1 = P-pA1 = 1.01325 x 105 – 74.0
= 1.01251 x 105 Pa, pB2 = 1.01325 x 105 – 0. since the values of
pB1 and pB2 are close to each other,
 Substituting into Eq. (6.2-32),

Example 6.2-5
Normal butanol (A) is diffusing through air (B)

at 1 atm abs. Using the Fuller et al. method,
estimate the diffusivity DAB for the following
temperatures with the experimental data:
(a) For 0 °C.
(b) For 25.9 °C.
(c) For 0 °C and 2.0 atm abs.

Solution
 For part (a), P = 1.00 atm, T = 273 + 0 = 273 K, MA (butanol) =
74.1, MB (air) = 29. From Table 6.2-2,
 Substituting into Eq. (6.2-45),
 This values deviates +10% from the experimental values of 7.03

x 10-6 m2/s from Table 6.2-1

 For part (b), T = 273 + 25.9 = 298.9. Substituting into Eq. (6.2-
45), DAB= 9.05 x 10-6 m2/s. This values deviates by +4% from the
experimental value of 8.70 x 10-6 m2/s
 For part (c), the total pressure P = 2.0 atm. Using the value
predicted in part (a) and correcting for pressure,
DAB = 7.73 x 10-6(1.0/2.0) = 3.865x10-6 m2/s

 Related molecular mass transfer
 Defined in terms of chemical potential:
dc DAB dc
v A, z  Vz  u A 
dz RT dz
 Nernst-Einstein relation
DAB d c
J A, z  c A (v A, z  Vz )  c A
RT dz

Diffusion Coefficient
 Fick’s law proportionality/constant
 J A, z M 1 L2
DAB   ( 2 )( )
dcAkinematic
 Similar to dz M L 1 Ln, and
3
L t viscosity, t
thermal diffusivity, a

 Gas mass diffusivity
 Based on Kinetic Gas Theory
1
DAA*  lu
3
 l = mean free path length, u = mean speed
2T 3 / 2  3N
DAA*  ( )1/ 2
 Hirschfelder’s
3  P M A
3/ 22
A
equation:
1/ 2
 1 1 
0.001858T   3/ 2

DAB   M A M B
P AB D
2

 Lennard-Jones parameters  and e from tables, or
from empirical relations
 for binary systems, (non-polar,non-reacting)
 A  B
 AB 
2
e AB  e Ae B
 Extrapolation of diffusivity up to 25 atmospheres
 P1  T2 
3/ 2
 D T1
DABT2 ,P2  DABT1 ,P1   
 P2  T1   D T2

Binary gas-phase Lennard-Jones
“collisional integral”

and 1/ 3
 1.585Vb 
 AB   A B  1/ 2
  2 
 1  1.3 
 For gas mixtures with several

components, 1
D1mixture  '
y2 / D12  y3' / D13  ...  yn' / D1n
 with y2
y 
'
y2  y3  ...  yn
2

2

 Pore diffusivity
 Diffusion of molecules within pores of
porous solids
 Knudsen diffusion for gases in cylindrical
pores
 Pore diameter smaller than mean
l free path, and
density of gas is low Kn 
d pore
 Knudsen number
 From Kinetic Theorylof l

8NT
u Gases,
DAA*  
3 3 M A
 But if Kn >1, then
d pore d pore 8NT T
DKA  u  4850 d pore
3 3 M A MA
 If both Knudsen and molecular diffusion exist, then
1 1  ay A 1
 
DAe DAB DKA
 with NB
a 1 
NA
 For non-cylindrical pores, we estimate
DAe  e DAe
' 2

Example 6

Types of porous diffusion. Shaded areas represent nonporous solids

 Hindered diffusion for solute in solvent-
filled pores
 A general model is
DAe  D F ( ) F2 ( )
o
AB 1
 F1 and F2 are correction factors, function of pore

diameter, ds

d pore
 F1 is the stearic partition

 (d pore coefficient
d s )2
F1 ( )   (1   ) 2
 d pore
2

 F2 is the hydrodynamic hindrance factor, one
equation is by Renkin,
F2 ( )  1  2.104  2.09 3  0.95 5

Example 7


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Mass transfer I

CHEG-212 MTO-I by KS Rajmohan

Treybal, R.E., ” Mass Transfer Operations “, McGraw-Hill Kogakusha, 1980.

CHEG-212 MTO-I by KS Rajmohan

CHEG-212 MTO-I by KS Rajmohan

CHEG-212 MTO-I by KS Rajmohan

CHEG-212 MTO-I by KS Rajmohan

Examples of industrial MTO:

G-G G-L G-S L-L L-S S-S

CHEG-212 MTO-I by KS Rajmohan

• Mass transfer refers to mass in transit due to a species concentration gradient

• Physical Origins of Diffusion:

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

 Transport of i relative to molar average velocity (v*) of mixture.

Ni : Absolute molar flux  kmol/s  m2  of species i.

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

CHEG-212 MTO-I by KS Rajmohan

• Mixture of Ideal Gases:

CHEG-212 MTO-I by KS Rajmohan

velocity of a particular species relative to mass/molar

CHEG-212 MTO-I by KS Rajmohan

CHEG-212 MTO-I by KS Rajmohan

Gases Liquid Solid

CHEG-212 MTO-I by KS Rajmohan

When drops of dye are added to a beaker of water, the

CHEG-212 MTO-I by KS Rajmohan

CHEG-212 MTO-I by KS Rajmohan

CHEG-212 MTO-I by KS Rajmohan

CHEG-212 MTO-I by KS Rajmohan

CHEG-212 MTO-I by KS Rajmohan

Transport processes in the environment may be

Diffusion works to eliminate sharp discontinuities in

CHEG-212 MTO-I by KS Rajmohan

Effusion is the process in which a

According to Graham's law, the rate at which gases effuse

CHEG-212 MTO-I by KS Rajmohan

Thomas Graham (1805–1869), a Scottish chemist, found

CHEG-212 MTO-I by KS Rajmohan

 Three fundamental transfer processes:

CHEG-212 MTO-I by KS Rajmohan

CHEG-212 MTO-I by KS Rajmohan

i) Number of molecules of each species

CHEG-212 MTO-I by KS Rajmohan

CHEG-212 MTO-I by KS Rajmohan

CHEG-212 MTO-I by KS Rajmohan

 The molecular transport process of mass is characterized

Rate of transfer process = driving force

CHEG-212 MTO-I by KS Rajmohan

CHEG-212 MTO-I by KS Rajmohan

CHEG-212 MTO-I by KS Rajmohan

is the molecular diffusivity of the molecule A in B in m2/s

z is the distance of diffusion in m

 The flux density j of particles has units e.g. #/(cm2s) or mol/(cm2s)

 The concentration is given in e.g. #/cm3 or mol/cm3

CHEG-212 MTO-I by KS Rajmohan

 Fick’s first law is a phenomenological – or empirical – expression; It

CHEG-212 MTO-I by KS Rajmohan

CHEG-212 MTO-I by KS Rajmohan

CHEG-212 MTO-I by KS Rajmohan

We will compare these two types of diffusion

The diffusion of molecules when the whole

CHEG-212 MTO-I by KS Rajmohan

A mixture of He and N2 gas is contained

CHEG-212 MTO-I by KS Rajmohan