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Slide No. 1 Slide No. 2

Lecture 6
DIFFUSION
MASS TRANSFER
Fundamentals
Dr. Dang Quoc Tuan
Dept Food Technology
International University
FOOD UNIT OPEARTIONS 2
Lecture Content
• Mass Transfer- Diffusion - Convection
• Concentration Gradient
• Mass Flux - Fick’s Law
• Mass Transfer by Diffusion
• Diffusivity
• Estimation of diffusivity
–Stoke-Einstein Equation
–Wilke-Change Eq.
–Hirschfelder’s Eq.
• Steady-state diffusion through solid /liquid
layer

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Slide No. 3 Slide No. 4

Mass Transfer
Examples of Mass Transfer
Mass transfer in industrial processes and
food processing
 A droplet of ink to fall into a stagnant pool of water • Carbonation of beverage
 Initially, the concentration of ink in the droplet is very • Gas or liquid permeation through packaging
high, and the concentration of ink in the water is zero, materials or membranes
thus establishing a concentration gradient. • Dispersion of gases into a fermentation broth
 As the ink migration continues, the concentration
• Removal of moisture from porous foods
gradient will decrease.
 When the ink becomes fully dissipated in the water, the • Extraction of active ingredients from plant tissues
concentration gradient becomes zero, and the mass • Dissolving sugar or salt in water
transfer process will cease. • Neutron diffusion within nuclear reactors
 The concentration gradient is considered the “ driving
force ”.
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Slide No. 5 Slide No. 6

Introduction of Mass Transfer Intro of Mass Transfer

 Mass transfer?
migration of a constituent of a fluid or a
component of a mixture.
 Cause?
changes in the physical equilibrium of the
system caused by the concentration differences.
 May occur within one phase or may involve
transfer from one phase to another.
 A bulk flow of a fluid from one location to
another: the process is not mass transfer.
Introduction to food engineering (Singh & Heldman)
Food Technology Department International University
 2nd of thermodynamics: systems tend to
move toward equilibrium with time.
 When a system contains two or more
components whose concentrations vary
from point to point, there is a natural
tendency for mass to be transferred,
minimizing the concentration differences
within a system.
 The transport of one constituent from a
region of higher concentration to that of a
lower concentration is called mass transfer.
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Slide No. 7 Slide No. 8

Modes of Mass Transfer Understand Diffusion?

Mass transfer involves:
• What is Diffusion?
 Diffusion at molecular scale
– process by which molecules, ions, or
 Bulk transport of mass due to convection flow
other small particles spontaneously mix,
moving from regions of relatively higher
• Convection
concentration into regions of lower
– Free convection: due to temperature concentration
differences which affect the density, and thus
relative buoyancy, of the fluid. • Diffusion in dilute solutions are frequently
– Forced convection: fluid movement results encountered
from external surface forces such as a fan or – diffusion in living tissue almost always involves the
pump transport of small amounts of solutes like salts,
antibodies, enzymes, or steroids.

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Slide No. 9 Slide No. 10

Mass transfer by diffusion Significance of Diffusion

When it is the slowest step in the sequence,
it limits the overall rate of the process
So, diffusion plays an important role in:
– commercial distillations
– rate of reactions using porous catalysts
– speed with which the human intestine absorbs
nutrients
– the growth of microorganisms producing penicillin
– rate of the corrosion of steel
– the release of flavor from food

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Slide No. 11 Slide No. 12

Early Work in Diffusion Flow Rate & Flux

Thomas Graham (University of Mass Flow Rate =
Glasgow)
 diffusion of gases (1828 ~ 1833);
constant pressure Mass: in kg or moles
 the tube filled with H2 gas, the level of
water in the tube slowly raised, Mass Flux =
because the H2 molecules inside the
tube escape through the holes in the
plaster more rapidly than the Volumetric Flow Rate =
molecules in air can enter the tube
 the rate of the water level raising ~
the rate at which different gases Volumetric Flux =
mixed with air SI Units:
 Graham's law of diffusion: the rates at
which gases diffuse is inversely
proportional to the square root of
their densities. Engineering Units:

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Slide No. 13 Slide No. 14

Mass Concentration Molar Concentration

in a multi-component mixture • CA is defined as the number of moles of A present per unit
volume of the mixture.
• For species A, mass concentration denoted by A is
defined as the mass of A, mA per unit volume of the
mixture.

•For ideal gas mixtures:

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

The total molar concentration or molar density of the mixture

is given by:

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Slide No. 15 Slide No. 16

Mole and Mass Fraction Bulk Velocities

For liquid and solid mixture – xA • In a multi-component system the various species will normally
For gaseous mixtures - yA move at different velocities;
• Velocity of mixture = averaging of the velocities of each
species present
• mass-average velocity for a multi-component mixture:
(liquids and solids)

(gases)

by similar way, mass fraction of A in mixture is; Where:  i is the velocity of species i with respect to stationary
fixed coordinates,
•molar-average velocity of the mixture * is:

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Slide No. 17 Slide No. 18

Diffusion Velocity & Diffusion Flux Absolute Flux

• Absolute flux of species defined with reference to fixed
• Diffusion velocity of A is defined: A -  spatial coordinates, NA :

(1)
• Average velocity of
mixture, : • It is a vector quantity.
• Amount (kg or mole) of A per unit of time through a unit area perpendicular
to the direction of transfer.

• This could be written in terms of diffusion velocity of A, (i.e.,  A - ) and

• Diffusion flux = mass flux of A relative to the mixture average velocity of mixture, , as:
mass-average velocity, JA :
But

•Therefore, equation of flux becomes:

(2)

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Slide No. 19 Slide No. 20

Absolute Flux and Diffusion Flux in a Binary Models for Mass Transfer
System • Mass transfer: define the flux

• Two models:
– Fick’s law

– Mass transfer coefficient model

JA
NA = absolute mass flux
JA = mass flux due to diffusion

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Fick’s Law Slide No. 21 Slide No. 22

(Adolf Eugen Fick ~1855) Fick’s Law- Restrictive Conditions

Diffusion can be described on the same mathematical basis Fick’ law:
as Fourier’s law for heat conduction or Newton’s law for
momentum transfer:
 CA - the concentration of component A (kg/m3, mol/m3 )
 D - the mass diffusivity (m2/s)
 CA - the concentration of component A (kg/m3, mol/m3 )
 D - the mass diffusivity (m2/s)
In terms mole fraction:
Fourier’s law for heat
conduction:  Two restrictive conditions:
A - area (m2). (1) Ordinary diffusion: effect of temp., pressure gradient and
external forces negligible (isothermal, isobaric system).
Newton’s equation for shear- (2) Coordinates moving with the average velocity of the
stress–strain relationship: mixture

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Slide No. 23 Slide No. 24

Models for Diffusion in Gases and Fick’s Law Applied for a binary gas
Liquids mixture
Binary system of A and B
Equimolar Counter Diffusion A B A B

Diffusion of gases in an
For the partial pressure of gas A: enclosed chamber

A B A B

Since:
JA = JB
 DAB -diffusivity or diffusion coefficient for component A diffusing Fick’s Law for a gas:
through component B
 dCA/dZ - the concentration gradient in the Z-direction
Also: DAB = DBA

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Slide No. 25 Slide No. 26

Fick’s Law for a Binary Sytem Models for Diffusion in Gases and
Liquids
Fick’s first law: diffusion of component A in an isothermal, Binary system of A and B
isobaric system; an empirical relation. Diffusion of A through a stagnant layer of B
In only the Z direction:

By definition:

where DAB is diffusivity or diffusion coefficient for component A diffusing

through component B, and dCA/dZ is the concentration gradient in the Z-
direction

NA = Absolute mass flux

JA = Diffusion flux
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Food Unit Operations 2
JB = 0
DA -diffusivity or diffusion coefficient for component A diffusing
through component B
dCA/dZ - the concentration gradient in the Z-direction
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Slide No. 27 Slide No. 28

Diffusivity
 Fick’s law proportionality, DAB : mass diffusivity
(simply as diffusivity) or as the diffusion
Diffusivity coefficient.
 DAB has the dimension of L2/t.
(Diffusion coefficient)  Other transport properties:
 kinematic viscosity (momentum diffusivity),
( = /) in momentum transfer.
 thermal diffusivity, ( = k/Cp ) in heat transfer.
 Reported in cm2 /sec; the SI unit being m 2 /sec.
 Depends on pressure, temperature, and
composition of the system.

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Slide No. 29 Slide No. 30

Diffusion coefficient Diffusivity in Gases

General range of values of diffusivity:
m2/s
In Gases: 5 X 10–6 - 1 X 10-5 m2 / sec.
In Liquids: 10–6 - 10-9 m2 / sec.
In Solids: 5 X 10 –14 - 1 X 10-10 m2 / sec.
(strong function of temperature)
In polymer/glasses: ~ 10-12 m2/sec (strong
function of solute concentration)

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Slide No. 31 Slide No. 32

Diffusivity in Liquids
Diffusivity in Liquids • Much slower that in gases due to the high density of
the solvent and the greater chance for interactions
between the solute and solvent.
• Typical values of D for solute in liquid are 10-5 to 10-7
m2/s cm2/sec
• The value of D for a solute in a liquid depends on
temperature, viscosity of liquid and size and shape
of solute.
The value of D for various solutes (A) in liquid solvent (B) are shown
Diffusion in liquids at 20 oC
Solute Solvent DAB (cm 2/sec*10-5)
O2 water 1.80
Acetic acid water 0.88
Ethanol water 1.00
phenol water 0.84

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Slide No. 33 Slide No. 34

Dependence of Diffusivity in Gases Estimation of Diffusivity in Gases

Pressure dependence: Hirschfelder’s
Equation:
(for moderate ranges of pressures, up to
25 atm).
DAB – diffusivity in a binary system (cm2/s)
Temperature dependency: T (K) – temperature
P (atm)- pressure
MA, MB- molecular weight of solute and solvent

 Approximation бAB – collision diameter =

– inversely proportional to pressure
ΩD – diffusion collision integral (dimensionless) = ~1
– 1.5 to 1.8 power of the temperature
– vary with molecular weight However, data for σ1, σ2 are rare

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Slide No. 35 Slide No. 36

Example 1 Solution 1:
Evaluate the diffusion coefficient of carbon dioxide in air at 20oC Evaluate the diffusion coefficient of carbon dioxide in air at 20oC
and atmospheric pressure. Compare this value with the and atmospheric pressure. Compare this value with the
experimental value, measured at standard condition (D= 0.136 experimental value, measured at standard condition (D= 0.136
cm2/s. cm2/s.
Given:
σ (Å) for CO2 = 3.996 бAB – collision diameter =
σ (Å) for air = 3.617
ΩD = 1.047 Diffusion coefficient DAB : T = 293.15 K
M(CO2) = 44
M(air) = 29
(cm2/s)
(using Hirschfelder’s theory)

Experimental value: at standard condition D = 0.136 cm2/s.

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Slide No. 37 Slide No. 38

Estimation of Diffusivity in Gases Estimation of Diffusivity in Gases

Fuller’s -When no reliable s or available.
-Group contribution of diffusion molar Using Critical Properties:
Equation:
volumes:

TCB , TCB– critical temperatures of A, B ( K)

Temperatures of the gas T ( K); Pressure (atm) VCA, VCB – critical molar volume of A, B
Σν – summing atomic diffusion volume (cm3/mol) P (atm) - pressure
-given in Literature (Table) MA, MB - molecular weight
C: 15.9 H: 2.31
O: 6.11 N: 4.54 (Reid et al.)
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Slide No. 39 Slide No. 40

Diffusion Coefficients in Liquids Hydrodynamic Theory based

Stoke - Einstein equation
 Most values are close to 10-9 m2/sec, including
common organic solvents, mercury, and molten iron, • Most common basis for estimating diffusion
coefficients in liquids (accurate ~ 20%, Reid et al., 1977)
etc...
• Derived by assuming a rigid solute sphere diffusion in
 High molecular-weight solutes (like albumin and a continuum of solvent (ratio of the size of solute to
polystyrene) can be must slower ~10-11 m2/sec that of solvent > 5)
 Slow diffusion in liquid means that diffusion often
limits the overall rate of process occurring in the liquid Boltzmann’s constant kB =1.381 × 10-23 m2 kg s-2 K-1
 chemistry: rate of acid - base reaction
 physiology: rate of digestion Solute radius
 metallurgy: rate of surface corrosion
 industry: rate of liquid-liquid extractions
Solvent viscosity
 No rigorous theories
Friction coefficient of the solute
 Diffusion as molecules or ions

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Slide No. 41 Slide No. 42

Estimation of Diffusivity in Liquids

Wilke-Chang Equation:

ΦB- association factor of solvent B (dimensionless)

VA – molar volume of solute at its boiling temperatures
(cm3/mol)
T- temperature, K ΦB :
Water : 2.26
MB- molecular weight of solvent, g/mol Methanol: 1.9
μB -viscosity of solvent, cP Ethanol: 1.5 Methanol: 42.5 Ethylene: 49.4
DAB in cm2/s Unssociated: 1.0 Acetone: 77.5
(From Reid et al. )

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Slide No. 43 Slide No. 44

Estimation of molecular volume from

Example 2 (Wilke-Chang eq.)
volume increment by atom Estimate the liquid diffusion coefficient of ethanol in a dilute
solution of water at 10oC. Given:
VC = 14.8 (Reid et al.)
V = a.va + b.vb + c.vc +… VH = 3.7
CO = 7.4
μB = 1.3 cP (at 10oC)
Molar volume increment by atom (Reid et al.): MB = 18
VC = 14.8 Solution 2: ΦB =2.26
VH = 3.7 The molecular volume of ethanol is estimated as:
VO = 7.4
VCl = 24.6 VC2H5OH = 2 VC + 6VH + VO T = 10 oC = 283 K
VN= = 15.6
VF = 10.5 VC2H5OH = 2(14.8) + 6(3.7) + 7.4 = 59.2 (cm3/mol)
VI = 38.5
VS = 21

The experimentally reported value is 8.3x10-10 m2/s

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Slide No. 45 Slide No. 46

Steady diffusion across a thin Steady-state diffusion in gases/liquids

film One-dimensional diffusion, the mass transfer rate is:
 On each side of the film is a well-mixed solution
of one solute, c10 > c1l
Mass balance in the layer z:
l
c10
rate of rate of diffusion Conditions of steady-state diffusion:
Solute
accumulation
= diffusion into out of the layer • Concentrations at the boundaries must be constant
the layer at z at z + z with time
z c1l
• Mass diffusivities (D) are not influenced by magnitude
(steady state)
of concentration
z
• No temperature gradients exist within the liquid layer.
• The term AREA included in RESISTANCE

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Steady-state diffusion in gases/liquids Slide No. 47 Slide No. 48

Steady-state diffusion in solids

A B A B
Driving Force Resistance The mass transfer rate is:

Equimolar Counter Diffusion in gas:

Diffusion of (A) through stagnant gas (B): For a single wall For a composite wall
ΣR = total resistance
Resistance Surface Area
Equimolar Counter Diffusion in liquid:
Geometries:
Flat wall
Diffusion of (A) through stagnant liquid (B):

Z – wall thickness
Cylindrical wall
XB,LM – log mean mol fraction of
Cm = mean concentration of (A) (B)
and (B) PB,LM –log mean partial pressure of
R = gas constant (B) Spherical wall
ΣR = total resistance P – total pressure
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Slide No. 49 Slide No. 50

Steady-state diffusion in solids Steady-state diffusion through solid

One-dimensional diffusion, the the mass transfer rate is: One-dimensional diffusion

Flux:

Rectangular coordinates
Conditions of steady-state diffusion:
• Concentrations at the boundaries must be constant with time
Cylindrical shape • Diffusion is limited to molecular motion within the solid
• Mass diffusivities (D) are not influenced by magnitude of
concentration
• No temperature gradients exist within the solid.
Spherical shape
6A

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Slide No. 51 Slide No. 52

Example 3: Stagnant Layer Solution 3

Water vapor is diffusing through a stagnant film of air at towards a 30oC
Water vapor is diffusing through a stagnant film of air at 30oC towards a cold surface at 6oC, where it is condensed. Calculate the water vapor
cold surface at 6oC, where it is condensed. Calculate the water vapor diffusion flux if the pressure is 1 atm, the water vapor pressure 10 mm from the
diffusion flux if the pressure is 1 atm, the water vapor pressure 10 mm cold surface is 3 kPa, and the water vapor diffusion coefficient in the air is 0.26
from the cold surface is 3 kPa, and the water vapor diffusion coefficient cm2/s
Given:
in the air is 0.26 cm2/s
ΔZ = 0.01 m; T 1 = 30 oC; T 2 = 6 oC; P = 1 atm; PA,1 = 3000 Pa
D = 0.000026 m 2/s
Given: Assumption: Note:
ΔZ = 0.01 m -system at steady state R ≠ ΣR
T 1 = 30 oC
T 2 = 6 oC Diffusion Flux (diffusion through stagnant layer):
P (total) = 1 atm
PA,1 = 3000 Pa
D = 0.000026 m 2/s

PA,2 =??
m A = ??
(A) = water A – water R = gas constant:
(B) = air B- air 8314.34 (m 3.Pa/kmol.K)

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Slide No. 53 Slide No. 54

Solution 3 Solution 3
Water vapor is diffusing through a stagnant film of air at 30oC
towards a Water vapor is diffusing through a stagnant film of air at towards a 30oC
cold surface at 6oC, where it is condensed. Calculate the water vapor cold surface at 6oC, where it is condensed. Calculate the water vapor
diffusion flux if the pressure is 1 atm, the water vapor pressure 10 mm from the diffusion flux if the pressure is 1 atm, the water vapor pressure 10 mm from
cold surface is 3 kPa, and the water vapor diffusion coefficient in the air is 0.26 the cold surface is 3 kPa, and the water vapor diffusion coefficient in the
cm2/s air is 0.26 cm2/s
Given:
ΔZ = 0.01 m; T1 = 30 oC; T2 = 6 oC; P = 1 atm; PA2 = 3000 Pa Given:
D = 0.000026 m2/s ΔZ = 0.01 m; T1 = 30 oC; T2 = 6 oC; P = 1 atm; Pw1 = 3000 Pa
D = 0.000026 m2/s
Water vapor at a 6 oC cold surface (from Steam Table):
Log Mean Pressure of air:
PA2 = 935 Pa

Water vapor at point (2)- 10 mm from the cold surface:

PA1 = 3000 Pa

Partial pressure of air at (1): Substitute values, water vapor flux, nA:
PB1 = 101325 – 3000 = 98325 Pa
Partial pressure of air at (2):
PB2 = 101325 – 935 = 100390 Pa
A – water JA = 2.17 x 10-6 kmol/(s m 2)
B - air
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Slide No. 55 Slide No. 56

Example 4: Equimolar Counter Diffusion Solution 4
To maintain a pressure close to 1 atm, an industrial pipeline containing ammonia
To maintain a pressure close to 1 atm, an industrial pipeline containing
gas is vented to ambient air. Venting is achieved by tapping the pipe and
ammonia gas is vented to ambient air. Venting is achieved by tapping inserting a 3-mm diameter tube, which extends for 20 m into the atmosphere.
the pipe and inserting a 3-mm diameter tube, which extends for 20 m With the entire system operating at 25oC, determine the mass rate of ammonia
into the atmosphere. With the entire system operating at 25oC, lost to the atmosphere and the mass rate of contamination of the pipe with air.
determine the mass rate of ammonia lost to the atmosphere and the The binary diffusion coefficient of ammonia-air system is 0.28 cm2/s
mass rate of contamination of the pipe with air. The binary diffusion
coefficient of ammonia-air system is 0.28 cm2/s
It is about equimolar counter diffusion
Given: ammonia Air
ΔZ = 20 m
T = 25 oC D= 0.003 m Assumptions:
P = 1 atm -Steady state, one dimensional diffusion in tube
nA nB
DAB = 0.000028 m 2/s (A) (B) -Constant properties
MA = 17 kg/kmol Z=20 m
MB = 28.97 kg/kmol
-Uniform temperature and total pressure
-Negligible mol fraction of air in pipe, xB,0 << 1
-Negligible mol fraction of ammonia in the atmosphere, xA,L<<1
It is about equimolar counter diffusion

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Solution 4 Slide No. 57

Solution 4
Slide No. 58

To maintain a pressure close to 1 atm, an industrial pipeline containing ammonia
gas is vented to ambient air. Venting is achieved by tapping the pipe and
inserting a 3-mm diameter tube, which extends for 20 m into the atmosphere.
With the entire system operating at 25oC, determine the mass rate of ammonia
lost to the atmosphere and the mass rate of contamination of the pipe with air.
The binary diffusion coefficient of ammonia-air system is 0.28 cm2/s
To maintain a pressure close to 1 atm, an industrial pipeline containing ammonia
gas is vented to ambient air. Venting is achieved by tapping the pipe and
inserting a 3-mm diameter tube, which extends for 20 m into the atmosphere.
With the entire system operating at 25oC, determine the mass rate of ammonia
lost to the atmosphere and the mass rate of contamination of the pipe with air.
The binary diffusion coefficient of ammonia-air system is 0.28 cm2/s

Equation for mass transfer: It is a equimolar counter diffusion, so nA = nB

nB = 0.4x10-12 kmol/s = 1.46x10-9 kgmol/h

From assumptions, then PA1 = P; PA2 = 0: mB = 28.97 kg/kmol)(1.46x10-9 kgmol/h)= 4.23x10-8 kg/h
Substitute:

nA = 0.4x10-12 kmol/s = 1.46x10-8 kgmol/h

mA = 17 kg/kmol)(1.46x10-9 kgmol/h)= 2.48x10-8 kg/h
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Slide No. 59 Slide No. 60

Example 5: Diffusion in solid Example 5:

An aroma compound is encapsulated in a nonporous spherical particle
An aroma compound is encapsulated in a nonporous spherical made of a homogenous biopolymer film. Calculate the aroma release rate if
the particle diameter is 1 mm, the film thickness is 0.1 mm, the
particle made of a homogenous biopolymer film. Calculate the
concentration of the aroma compound is 0.1 g/cm3 and 0.01g/cm3 on the
aroma release rate if the particle diameter is 1 mm, the film inside and outside surface of the
thickness is 0.1 mm, the concentration of the aroma compound is particle respectively, and the diffusion coefficient of the aroma compound
0.1 g/cm3 and 0.01g/cm3 on the inside and outside surface of the in the film is 1x10-12 m2/s.
particle respectively, and the diffusion coefficient of the aroma
compound in the film is 1x10 -12 m2/s. Solution 5:
Step 1- Assumptions:
-The aroma release is diffusion –controlled
Given: -Steady-state diffusion (the rate of release is constant w/ time)
r1 = 0.0005 m
r2 = 0.0006 m Step 2- Resistance Calculation:
C1 = 0.1g/cm3 = 100 kg/m3
A1 = 4π r12 = 3.14 x 10-6 m 2
C2 = 0.01 g/cm3 = 10 kg/m3 ∆r
D = 1.0x10-12 m2/s A1 = 4π r22 = 4.52 x 10-6 m 2 RESISTANCE = R =
D.AG
AG = sqrt(A1.A2) = 3.77 x 10-6 m 2

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Slide No. 61 Slide No. 62

Solution 5:
Step 3- Diffusion rate through the spherical wall: Further Readings:
1. R. Paul Singh, Dennis R. Heldman. 2009. Introduction
to food engineering. Academic Press. 4th Edition.
(Ch. 10)
2. Robert C. Reid, John M. Prausnitz, Bruce E. Poling.
The Properties of Gases and Liquids. McGraw-Hill,
1987. (Ch. 5)

HW: 10.1, 10.2; 10.3 (S&H)

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