Mass Transfer

UNIT 3 MASS TRANSFER

Structure
3.1 Introduction
Objectives
3.2 Concentration
3.3 Examples of Mass Transfer Process
3.4 General Molecular Transport Equation
3.5 Physical Origins and Rate Equations
3.6 Mixture Composition
3.7 Fick’s Law of Diffusion (Vector Form)
3.8 Restrictive Conditions
3.9 Convective Mass Transfer
3.10 Types of Mass-Transfer Coefficients
3.10.1 Definition of Mass-Transfer Coefficient
3.10.2 Mass-Transfer Coefficient for Equimolar Counter Diffusion
3.10.3 Mass-Transfer Coefficient for A Diffusing through Stagnant, Non-diffusing B
3.11 Summary
3.12 Key Words
3.13 Answers to SAQs

3.1 INTRODUCTION
We have learned that heat is transferred if there is temperature difference in a medium.
Similarly, if there is a difference in the concentration of some chemical species in a
mixture, mass transfer must occur. Mass transfer is mass in transit as the result of a
species concentration difference in a mixture.
Just as a temperature gradient constitutes the driving potential for heat transfer, a species
concentration gradient in a mixture provides the driving potential for transport of the
species.
It is important to understand clearly the context in which the term mass transfer is used.
Although mass is certainly transferred whenever there is bulk fluid motion, this is not
what we have in mind. For example, we do not use the term mass transfer to describe the
motion of air that is induced by a fan or the motion of water being forced through a pipe.
In both cases, there is gross or bulk fluid motion due to mechanical work. We do,
however, use the term to describe the relative motion of species in a mixture due to the
presence of concentration gradients. One example is the dispersion of oxides of sulfur
released from a power plant smoke stake into the environment. Another example is the
transfer of water vapour into dry air, as in a home humidifier.
There are modes of mass transfer that are similar to the conduction and convection modes
of heat transfer. Mass transfer may occur by diffusion or by convection. Mass transfer by
diffusion is analogous to conduction heat transfer.
Mass transfer occurs in distillation, absorption, drying, liquid-liquid extraction,
adsorption and membrane processes. When mass is being transferred from one distinct
phase to another or through a single phase, the basic mechanisms are same whether the
phase is a gas, liquid or solid. Mass, heat and momentum transfer processes are similar.

63
Introduction to Heat Objectives
and Mass Transfer
After studying this unit, you should be able to
• understand the principle of mass transfer,
• recognise the physical origin and rate equation describing mass transfer,
• distinguish different modes of mass transfer (molecular diffusion and
convective mass transfer),
• recognise the applications of mass transfer processes,
• determine mass transfer in various specific cases,
• evaluate mass transfer coefficient, and
• apply theory in solving simple mass transfer problems.

3.2 CONCENTRATION
The concentration of a chemical solution refers to the amount of solute that is dissolved
in a solvent. We normally think of a solute as a solid that is added to a solvent (e.g.
adding table salt to water), but the solute could just as easily exist in another phase. For
example, if we add a small amount of ethanol to water, then the ethanol is the solute and
the water is the solvent. If we add a smaller amount of water to a larger amount of
ethanol, then the water could be the solute.
3.2.1 Units of Concentration
Once we have identified the solute and solvent in a solution, we are ready to determine
its concentration. Concentration may be expressed several different ways, using percent
composition by mass, mole fraction, molarity, molality, or normality.
Percent Composition by Mass (%)
This is the mass of the solute divided by the mass of the solution (mass of solute
plus mass of solvent), multiplied by 100.
Example
Determine the percent composition by mass of a 100 g salt solution which contains
20 g salt.
Solution
20 g NaCl/100 g solution × 100 = 20% NaCl solution.
Mole Fraction (X)
This is the number of moles of a compound divided by the total number of moles
of all chemical species in the solution. Keep in mind, the sum of all mole fractions
in a solution always equals 1.
Example
What are the mole fractions of the components of the solution formed when 92 g
glycerol is mixed with 90 g water? (Molecular weight water = 18; molecular
weight of glycerol = 92).
Solution
90 g water = 90 g × 1 mol/18 g = 5 mol water
92 g glycerol = 92 g × 1 mol/92 g = 1 mol glycerol
Total mol = 5 + 1 = 6 mol
xwater = 5 mol/6 mol = 0.833
xglycerol = 1 mol/6 mol = 0.167
64
 It’s a good idea to check your math by making sure the mole fractions add up to Mass Transfer
1 : xwater + xglycerol = 0.833 + 0.167 = 1.000
Molarity (M)
Molarity is probably the most commonly used unit of concentration. It is the
number of moles of solute per liter of solution (not necessarily the same as the
volume of solvent!).
Example
What is the molarity of a solution made when water is added to 11 g CaCl2 to
make 100 mL of solution?
Solution
11 g CaCl2/(110 g CaCl2/mol CaCl2) = 0.10 mol CaCl2
100 mL × 1 L/1000 mL = 0.10 L
Molarity = 0.10 mol/0.10 L
Molarity = 1.0 M
Molality (m)
Molality is the number of moles of solute per kilogram of solvent. Because the
density of water at 25°C is about 1 kilogram per liter, molality is approximately
equal to molarity for dilute aqueous solutions at this temperature. This is a useful
approximation, but it should be remembered that it is only an approximation and
doesn’t apply when the solution is at a different temperature, is not dilute, or uses a
solvent other than water.
Example
What is the molality of a solution of 10 g NaOH in 500 g water?
Solution
10 g NaOH/(4 g NaOH/1 mol NaOH) = 0.25 mol NaOH
500 g water × 1 kg/1000 g = 0.50 kg water
Molality = 0.25 mol/0.50 kg
Molality = 0.05 M/kg
Molality = 0.50 m
Normality (N)
Normality is equal to the gram equivalent weight of a solute per liter of solution. A
gram equivalent weight or equivalent is a measure of the reactive capacity of a
given molecule. Normality is the only concentration unit that is reaction
dependent.
Example
1 M sulfuric acid (H2SO4) is 2 N for acid-base reactions because each mole of
sulfuric acid provides 2 moles of H+ ions. On the other hand, 1 M sulfuric acid is
1 N for sulfate precipitation, since 1 mole of sulfuric acid provides 1 mole of
sulfate ions.
Dilutions
We dilute a solution whenever we add solvent to a solution. Adding solvent results
in a solution of lower concentration. We can calculate the concentration of a
solution following a dilution by applying this equation :
Mi Vi = Mf Vf
where M is molarity, V is volume, and the subscripts i and f refer to the initial and
final values.
65
Introduction to Heat Example
and Mass Transfer
How many millilieters of 5.5 M NaOH are needed to prepare 300 mL of 1.2 M
NaOH?
Solution
5.5 M × V1 = 1.2 M × 0.3 L
V1 = 1.2 M × 0.3 L/5.5 M
V1 = 0.065 L
V1 = 65 mL
So, to prepare the 1.2 M NaOH solution, you pour 65 mL of 5.5 M NaOH into
your container and add water to get 300 mL final volume.
SAQ 1
Define the following :
(i) Mole fraction
(ii) Dilution
(iii) Normality
(iv) Molality
(v) Molarity

3.3 EXAMPLES OF MASS TRANSFER PROCESS

Mass transfer is important in many areas of science and engineering. Mass transfer
occurs when a component in a mixture migrates in the same phase or from phase to phase
because of a difference in concentration between two points. Many familiar phenomena
involve mass transfer. Some examples are :
(a) Liquid in an open pail of water evaporates into still air because of the
difference in concentration of water vapour at water surface and the
surrounding air. There is driving force from surface to the air.
(b) A cube of sugar added to a cup of coffee eventually dissolves by itself and
diffuses to the surrounding solution.
(c) When a newly cut moist green timber is exposed to atmosphere, the wood
will dry partially when moisture in the timber diffuses through the wood, to
the surface, and then to the atmosphere.
(d) In a fermentation process nutrients and oxygen dissolved in the solution
diffuse to the microorganisms.
(e) In a catalytic reaction the reactants diffuse from the surrounding medium to
the catalyst surface where the reaction occurs.
(f) Mass transfer process occurs in the uranium processing. In such a process,
uranium salt in solution is extracted by an organic solvent.
We can treat mass transfer in a manner some what similar to that used in heat transfer
with Fourier law of conduction. However, an important difference between the two is
that in molecular mass transfer one or more of the components of the medium is moving.
In heat transfer by conduction the medium is usually stationary and the only energy in
the form of heat is being transported.
66
 Mass Transfer
3.4 GENERAL MOLECULAR TRANSPORT EQUATION
All three molecular transport processes (heat, momentum and mass transfer) are
characterized by the same general type of equation as indicated in unit 1.
driving force
Rate of a transport process = . . . (3.1)
resistance
This can be written as follows for molecular diffusion of the property momentum, heat,
and mass
dΓ
ψz = − δ . . . (3.2)
dz
Molecular diffusion equation for momentum, heat and mass transfer.
Newton’s equation for momentum transfer for constant density can be written as follows
in a manner similar to Eq. (3.2).
μ d
τ zx = − ( v x ρ) . . . (3.3)
ρ dz
μ
where τzx is momentum transferred/s.m2, = kinematic viscosity in m2/s, z = distance
ρ
in m, and vx ρ = momentum per m , where the momentum has units of kg.m/s.
3

Fourier’s law for heat conduction can be written for constant ρ and Cp as
qz d
=−α (ρ C p T ) . . . (3.4)
A dz
qz
where is the heat flux in W/m2, α is the thermal diffusivity in m2/s and ρC pT
A
in J/m3.
The equation for molecular diffusion of mass is called the Fick’s law and is similar to Eq.
(3.2). It is written for constant total concentration in a fluid as
d CA
J *Az = − DAB . . . (3.5)
dz
where J*Az is the molar flux component A in the z direction due to molecular diffusion in
kg mol A/s.m2, DAB is the molecular diffusivity of the molecule A in B in m2/s, CA is the
concentration of A in kg mol/m3, and z is the distance of diffusion in m.
The similarity of Eqs. (3.3)-(3.5) for momentum, heat and mass transfer is obvious. All
the fluxes on the left hand side of the three equations have as units transfer of a quantity
of momentum, heat or mass per unit time per unit area.

The transport properties μ , α and DAB all have units of m2/s, and the concentrations are
ρ
represented as momentum/m3, J/m3 or kg mol/m3.

3.5 PHYSICAL ORIGINS AND RATE EQUATIONS

From the standpoint of physical origins and the governing rate equations, strong
analogies exist between heat and mass transfer by diffusion.
3.5.1 Physical Origins
Both conduction heat transfer and mass diffusion are transport processes that originate
from molecular activity. Consider a chamber in which two different gas species at the
same temperature and pressure are initially separated by a partition. If the partition is
67
Introduction to Heat removed, both species will be transferred by diffusion. Figure 3.1 shows the situation as
and Mass Transfer it might exist shortly after removal of the partition.

CA CB
Concentration of Concentration of
Species A Species B

ZD
Z

Figure 3.1 : Mass Transfer by Diffusion in a Binary Gas Mixture

A higher concentration means more molecules per unit volume, and the concentration of
species A (light dots) decreases with increasing z, while the concentration of B increases
with z. Since mass diffusion is in the direction of decreasing concentration, there is net
transport of species A to the right and of species B to the left. The physical mechanism
may be explained by considering the imaginary plane show as a dashed line at z0. Since
molecular motion is random, there is equal probability of any molecule moving to the left
or the right. Accordingly, more molecules of species A cross the plane from the left
(since this is the side of higher A concentration) than from the right. Similarly, the
concentration of B molecules is higher to the right of the plane than to the left, and
random motion provides for net transfer of species B to the left. Of course, after a
sufficient time, uniform concentrations of A and B are achieved, and there no net
transport of species A and B across the imaginary plane.
Mass diffusion occurs in liquids and solids, as well as in gases. However, since mass
transfer is strongly influenced by molecular spacing, diffusion occurs more readily in
gases than in liquids and more readily in liquids than in solids. Examples of diffusion
gases, liquids, and solids, respectively, include nitrous oxide from an automobile exhaust
in air, dissolved oxygen in water, and helium in Pyrex.

3.6 MIXTURE COMPOSITION

A mixture consists of two or more chemical constituents (species), and the amount of any
species i may be quantified in terms of its mass density ρi (kg/m3) and molar
concentration Ci (k mol/m3). The mass density and molar concentration are related
through the species molecular weight, Mi (kg/k mol), such that
ρi = M i Ci . . . (3.6)

68
With ρi representing the mass of species i per unit volume of the mixture, the mixture Mass Transfer
mass density is
ρ = ∑ ρi . . . (3.7)
i

Similarly, the total number of moles per unit volume of the mixture is
C = ∑ Ci . . . (3.8)
i

The amount of species i in a mixture may also be quantified in terms of its mass fraction
ρi
mi = . . . (3.9)
ρ
or its mole fraction
Ci
xi = . . . (3.10)
C
From Eqs. (3.7) and (3.8), it follows that
∑ mi = 1 . . . (3.11)
i

and ∑ xi = 1 . . . (3.12)
i

For a mixture of ideal gases, the mass density and molar concentration of any constituent
are related to the partial pressure of the constituent through the ideal gas law. That is,
Pi
ρi = . . . (3.13)
Ri T
Pi
and Ci = . . . (3.14)
RT
where Ri is the gas constant for species i and R is the universal gas constant. Using
Eqs. (3.10) and (3.14) with Delton’s law of partial pressures,
P = ∑ Pi . . . (3.15)
i

It follows that
Ci Pi
xi = = . . . (3.16)
C P

3.7 FICK’S LAW OF DIFFUSION (VECTOR FORM)

Since the same physical mechanism is associated with heat and mass transfer by
diffusion, it is not surprising that the corresponding rate equations are of the same form.
The rate equation for mass diffusion is known as Fick’s law, and for the transfer of
species A in a binary mixture of A and B, it may be expressed in vector form as
j A = − ρ DAB ∇ m A . . . (3.17)

or J ∗A = − CDAB ∇ x A . . . (3.18)
These expressions are analogous to Fourier’s law, Eq. (2.3). Moreover, just as Fourier’s
law serves to define one important transport property, the thermal conductivity, Fick’s
law defines a second important transport property, namely, the binary diffusion
coefficient or mass diffusivity, DAB.
The quantity jA (kg/s.m2) is defined as the mass flux of species A. It is the amount of A
that is transferred per unit time and per unit area perpendicular to the direction of
transfer, and it is proportional to the mixture of mass density, ρ = ρ A + ρ B (kg/m3 ) , and
69
Introduction to Heat ρA
and Mass Transfer to the gradient in the species mass friction, mA = . The species flux may also be
ρ
evaluated on a molar basis, where J*A (k mol/s.m2) is the molar flux of the species A. It is
proportional to the total molar concentration of the mixture, C = CA + CB (k mol/m3), and
B

C
to the gradient in the species mole fraction, x A = A1 . The foregoing forms of Fick’s law
C
may be simplified with the total mass density ρ or the total molar concentration C is a
constant.
SAQ 2
(a) Define Fick’ s law of diffusion.
(b) Explain how does diffusion take place?

3.8 RESTRICTIVE CONDITIONS

Despite its analogous behaviour, mass diffusion, a good deal, more complicated than
conduction. Complications are associated with two restrictive conditions inherent in
Eqs. (3.17) and (3.18). First although mass diffusion may result from a temperature
gradient, a pressure gradient, or an external force, as well as from a concentration
gradient, we are assuming that these additional effects are not present or are negligible. In
most problems, this is in fact the case, and the dominant driving potential in the species
concentration gradient. This condition is referred to as ordinary diffusion. Treatment of
the other (higher order) effects is presented by Bird, et al. [1-3].
The second restrictive condition is that the fluxes are measured relative to coordinates
that move with the average velocity of the mixture. If the mass or molar flux of a species
is expressed relative to a fixed set of coordinates. Eqs. (3.17) and (3.18) are not generally
valid.
To obtain an expression for the mass flux relative to a fixed coordinates system, consider
species A in binary mixture of A and B. The mass flux n nA relative to a fixed coordinate
system is related to the species absolute velocity VA by

n nA ≡ ρ A VA . . . (3.19)
A value of VA may be associated with any point in the mixture, and it is interpreted as the
average velocity of all the A. Particulars in a small volume element about the point. An
average or an aggregate, velocity may also be associated with the particulars of species B
in which case

nBn ≡ ρ B VB . . . (3.20)
A mass-average velocity for the mixture may than be obtained from the requirement that

ρV = n n = n nA + nBn = ρ A VA + ρ B VB . . . (3.21)

giving U = m A VA + mB VB . . . (3.22)
It is important to note that we have defined the velocities (VA, VB, V) and the fluxes
B

n′′A , nB′′ , n′′ as absolute quantities. That is, they are referred to axes that are fixed in
space. The mass average velocity V is a useful parameter of the binary mixture, since it
need to be multiplied by the total mass density to obtain the total mass flux with respect
to fixed axes. Moreover, since the velocities VA, VB and V are averages associated with
B

70
aggregates of particles, the fluxes n′′A , nB′′ and n′′ may be associated with transport due to Mass Transfer

bulk or gross motion.

We may now define the mass flux of species A relative to the mixture mass-average
velocity as
j A ≡ ρ A (VA − V ) . . . (3.23)
Whereas n′′A is the absolute flux of species A, jA.is the relative or diffusive flux of the
species. It represents the motion of the species relative to the average motion of the
mixture. It follows from Eq. (3.19) that
n′′A = j A + ρ A V . . . (3.24)
This expression indicates that there are two contributions to the absolute flux of species A
: a contribution due to diffusion (i.e. due to the motion of a relative to the
mass-average motion of the mixture) and a contribution due to motion of A with the
mass-average motion of the mixture. Substituting from Eqs. (3.17) and (3.21), we obtain
n′′A = − ρ DAB ∇m A + mA (n′′A + nB′′ ) . . . (3.25)
At this point it is useful to recap what we have done by noting the alternative
formulations for the mass flux of species A. The form given by Eq. (3.17) determines the
transport of A relative to the mixture mass-average velocity, whereas the form given by
Eq. (3.25) determines the absolute transport of A. If the second term on the right hand
side of the Eq. (3.25) is not zero, the expression for absolute flux of species A.
Eq. (3.25), is not analogous to that for heat flux, Eq. (2.3).
The foregoing considerations may be extended to species B. The mass flux of B relative
to the mixture mass-average velocity (the diffusive flux) is
jB ≡ ρ B (VB − V ) . . . (3.26)
where jB = − ρ DBA ∇mB . . . (3.27)
It follows from Eqs. (3.17), (3.23), and (3.26) that the diffusive fluxes in a binary mixture
are related by
j A + jB = 0 . . . (3.28)
If Eqs. (3.17) and (3.27) are substituted into Eq. (3.18), and it is recognized that
∇m A = − ∇mB , since mA + mB = 1 for a binary mixture, it follows that
B

DBA = DAB . . . (3.29)

Hence, as in Eq. (3.25), the absolute flux of species B may be expressed as :
nB′′ = − ρ DAB ∇mB + mB (n′′A + nB′′ ) . . . (3.30)
Although the foregoing expressions pertain to mass fluxes, the same procedures can be
used to obtain results on a molar basis. The absolute molar fluxes of species A and B may
be expressed as
N ′′A ≡ C A VA . . . (3.31)
and N B′′ ≡ CB VB . . . (3.32)
and a molar-average velocity for the mixture, V*, is obtained from the requirement that

N ′′ = N ′′A + N B′′ = CV * = C A VA + CB VB . . . (3.33)

Giving V * = x A VA + xB VB . . . (3.34)

The significance of the molar average velocity is that, when multiplied by the total molar
concentration C, it provides the total molar flux N″ with respect to a fixed coordinate
system. Eqs. (3.31) and (3.32) provide the absolute molar flux of species A and B. In 71
Introduction to Heat contrast, the molar flux of A relative to the mixture molar average velocity J*A, termed the
and Mass Transfer diffusive flux, may be obtained from Eq. (3.17) or from the expression

J *A ≡ C A (VA − V * ) . . . (3.35)

To determine an expression similar in form to Eq. (3.25), we combine Eqs. (3.31), (3.32)
and (3.35) to obtain

N ′′A = J *A + C A V * . . . (3.36)

or, from Eqs. (3.18) and (3.33),

N ′′A = − CDAB ∇x A + x A ( N ′′A + N B′′ ) . . . (3.37)

Compare the molar fluxes given by Eqs. (3.18) and (3.37). In the first case the molar flux
is relative to the mixture molar-average velocity, and in the second case it is the absolute
molar flux. Note also that Eq. (3.37) represents the absolute molar flux as the sum of a
diffusive flux and a flux due to the bulk motion of the mixture. For the binary mixture, it
also follows that

J *A + J B* = 0 . . . (3.38)

A special case for which the absolute flux of a species is equal to the diffusive flux
pertains to what is termed a stationary medium. In terms of mass units, it is a medium for
which V = 0, in which case j A = n′′A . In terms of molar units, it is a medium for which
V* = 0 and hence J ′′A = N ′′A . For this special case, the analogy between heat and mass
transfer is complete, since the rate equations have the same physical form regardless of
the reference frame.

3.9 CONVECTIVE MASS TRANSFER

In the previous sections of this unit we have emphasized molecular diffusion in stagnant
fluids or fluids in laminar flow. In many cases the rate of diffusion is slow, and more
rapid transfer is desired. To do this, the fluid velocity is increased until turbulent mass
transfer occurs.
To have a fluid in convective flow usually requires the fluid to be flowing by another
immiscible fluid or by a solid surface. An example is a fluid flowing in a pipe, where part
of the wall pipe is made by a slightly dissolving solid material such as benzoic acid. The
benzoic acid dissolves and is transported perpendicular to the main stream from the wall.
When a fluid is in turbulent flow and is flowing past a surface, the actual velocity of
small particles of fluid cannot be described clearly as in laminar flow. In laminar flow the
fluid flows in streamlines and its behaviour can usually be described mathematically.
However, in turbulent motion there are no streamlines, but there are large eddies or
“chunks” of fluid moving rapidly in seemingly random fashion.
When a solute A is dissolving from a solid surface there is a high concentration of this
solute in the fluid at the surface, and its concentration, in general, decreases as the
distance from the wall increases. However, minute samples of fluid adjacent to each other
do not always have concentrations close to each other. This occurs because eddies having
solute in them move rapidly from one part of the fluid to another, transferring relatively
large amounts of solute. This turbulent diffusion or eddy transfer is quite fast in
comparison to molecular transfer.
When a fluid is flowing outside a solid surface in forced convection motion, we can
express the rate of convective mass transfer from the surface to the fluid, or vice-versa,
by the following equation
N A = k c (C L1 − C L 2 ) . . . (3.39)

72
where kc is the convective mass transfer coefficient in m/s, CL1 is the bulk fluid Mass Transfer
concentration in kg mol A/m3, CL2 is the concentration in the fluid next to the surface of
the solid. This mass transfer coefficient is very similar to the heat transfer coefficient h
and is a function of the system geometry, fluid properties, and flow velocity.
Three regions of mass transfer can be visualized. In the first, which is adjacent to the
surface, a thin viscous sub layer film is present. Most of the mass transfer occurs by
molecular diffusion, since few or no eddies are present. A large concentration drop
occurs across this film as a result of the slow diffusion rate.
The transition or buffer region is adjacent to the first region. Some eddies are present and
the mass transfer is the sum of turbulent and molecular diffusion. There is a gradual
transition in this region from the transfer by mainly molecular diffusion at the one end to
mainly turbulent at the other end.
In the turbulent region adjacent to the buffer region, most of the transfer is by turbulent
diffusion, with a small amount by molecular diffusion. The concentration decreases is
very small here since the eddies tend to keep the fluid concentration uniform. A typical
plot for the mass transfer of a dissolving solid from a surface to a turbulent fluid in a
conduit is given in Figure. 3.2.

CA 1

CA

CA 2

O z
Distance from Surface
Figure 3.2 : Concentration Profile in Turbulent Mass Transfer from a Surface to a Fluid

The concentration drop from cA1 adjacent to the surface is very abrupt close to the surface
and then levels off. This curve is very similar to the shapes found for heat and
momentum transfer. The average or mixed concentration c A is shown and is slightly
greater than the minimum cA2.
SAQ 3
(a) Distinguish between the molecular diffusion and convective mass transfer.
(b) What is turbulent mass transfer?
(c) How does the concentration profile changes in case of turbulent mass
transfer?

3.9.1 Mass Diffusion Coefficient

Considerable attention has been given to predicting the mass diffusion coefficient DAB for
the binary mixture of two gasses, A and B. Assuming ideal gas behaviour, kinetic theory
may be used to show that
3
−1
DAB ~ p T2 . . . (3.40)
73
Introduction to Heat This relation applies for restricted pressure and temperature ranges and is useful for
and Mass Transfer estimating values of the diffusion coefficient at condition other than those for which data
are available. Bird, et al. [1 – 3] provide detail discussion of available theoretical
treatments and compressions with experiment.
For binary liquid solution, it is necessary to rely exclusively on experimental
measurements. For small concentration of A (the solute) in B (the solvent), DAB is known
to increase with increasing temperature. The mechanism of diffusion of gases, liquids and
solids in solids is extremely complicated and generalized theories are not available.
Furthermore, only limited experimental results are available in literature.
Data for binary diffusion in selected mixtures are presented in Table 3.1.
Table 3.1 : Binary Diffusion Coefficients at One Atmosphere
Substance A Substance B T DAB
(K) (m2/s)
Gases
NH3 Air 2982 0.28 × 10– 4
H2O Air 298 0.26 × 10– 4
CO2 Air 298 0.16 × 10– 4
H2 Air 298 0.41 × 10– 4
O2 Air 298 0.21 × 10– 4
Acetone Air 273 0.11 × 10– 4
Benzene Air 287 0.88 × 10– 5
Naphthalene Air 300 0.62 × 10– 5
Ar N2 293 0.19 × 10– 4
H2 O2 273 0.70 × 10– 4
H2 N2 273 0.68 × 10– 4
H2 CO2 273 0.55 × 10– 4
CO2 N2 293 0.16 × 10– 4
CO2 O2 273 0.14 × 10– 4
O2 N2 273 0.18 × 10– 4
Dilute Solutions
Caffeine H2O 298 0.63 × 10– 9
Ethanol H2O 298 0.12 × 10– 8
Glucose H2O 298 0.69 × 10– 9
Glycerol H2O 298 0.94 × 10– 9
Acetone H2O 298 0.13 × 10– 8
CO2 H2O 298 0.20 × 10– 8
O2 H2O 298 0.24 × 10– 8
H2 H2O 298 0.63 × 10– 8
H2 H2O 298 0.26 × 10– 8
Solids
O2 Rubber 298 0.21 × 10– 9
N2 Rubber 298 0.15 × 10– 9
CO2 Rubber 298 0.11 × 10– 9
He SiO2 293 0.4 × 10– 13
H2 Fe 293 0.26 × 10– 12
Cd Cu 293 0.27 × 10– 18
Al Cu 293 0.13 × 10– 33

74
SAQ 4 Mass Transfer

Show that for a equimolar counter diffusion of two species A and B

DAB = DBA

3.10 TYPES OF MASS-TRANSFER COEFFICIENTS

3.10.1 Definition of Mass-Transfer Coefficient
Since our understanding of turbulent flow is incomplete, we attempt to write the
equations for turbulent diffusion in a manner similar to that for molecular diffusion. For
turbulent mass transfer for constant c,
dc A
J ∗A = − ( DAB + ε M ) . . . (3.41)
dz
where DAB is the molecular diffusivity in m2/s and εM is the mass eddy diffusivity in m2/s.
The value of εM is a variable and is near zero at the interface or surface and increases as
the distance from the wall increases. We then use an average value εM since the
variation of εM is not generally known. Integrating Eq. (3.41) between points 1 and 2,
DAB + εM
J ∗A1 = (c A1 − c A2 ) . . . (3.42)
z2 − z1

The flux J ∗A1 is based on the surface area A1 since the cross-sectional area may vary. The
value of z2 – z1, the distance of the path, is often not known. Hence, Eq. (3.42) is
simplified and is written using a convective mass-transfer coefficient k′c.

J ∗A1 = kc′ (c A1 − c A2 ) . . . (3.43)

where J ∗A1 is the flux of A from the surface A1 relative to the whole bulk phase, k′c is
( DAB + εM )
an experimental mass transfer coefficient in kg mol/s.m2. (kg mol/m3) or
( z2 − z1 )
simplified as m/s, and cA2 is the concentration at point 2 in kg mol A/m3 or more usually
the average bulk concentration c A2 . This defining of a convective mass-transfer
coefficient k′c is quite similar to the convective heat-transfer coefficient h.
3.10.2 Mass-Transfer Coefficient for Equimolar Counter Diffusion
Figure 3.3 presents the phenomenon of equimolar counterdiffusion of gases. Gases A and
B are kept in the two chambers connected by a tube at a total pressure p. Assume
molecular diffusion to be under a steady state condition. In order to maintain uniform
concentration of gases, both the chambers are stirred continuously. Let, the partial
pressures be pA1 > pA2 and pB1 > pB2.
Molecules of A diffuse to the right and B to the left. Since the total pressure p is constant
throughout, the net moles of A diffusing to the right must be equal to the net moles of B
to the left. If this is not so, the total pressure would not remain constant. This means that

J *Az = − J Bz
*
. . . (3.44)
75
Introduction to Heat
and Mass Transfer

PA1 PA2

1 2
PB1 PB 2
*
P J A P
*
J B

P
PA1
PB2
PA, PB, or P
PA2
PB1

Figure 3.3 : Equimolar Counter Diffusion of Gases A and B

The subscript z is dropped when the direction is obvious. Writing Fick’s law for B for
constant c

dcB
J B* = − DBA . . . (3.45)
dz
Now since p = pA + pB constant, then
B

c = c A + cB . . . (3.46)

Differentiating both sides,

dc A = − dcB . . . (3.47)

Equating Eqs. (3.18) to (3.45),

dc A dc
J *A = − DAB = − J B* = − (−) DBA B . . . (3.48)
dz dz
Substituting Eq. (3.47) into Eq. (3.48) and canceling like terms,

DAB = DBA . . . (3.49)

This shows that for a binary gas mixtures of A and B the diffusivity coefficient DAB for A
diffusing in B is the same as DBA diffusing into A.

3.10.3 Mass-Transfer Coefficient for A Diffusing through Stagnant,

Non-diffusing B
The case of diffusion of A through stagnant or non-diffusing B at steady state often
occurs. In this case, one of the boundaries at the end of the diffusion path is impermeable
to component B and hence the species B cannot pass through it. Figure 3.4 presents the
evaporation of a pure liquid such as benzene (say, species A) at the bottom of a narrow
tube, where a large amount of inert or non-diffusing air (species B) is passed over the top.
The benzene vapour (A) diffuses through the air (B) in the tube. The boundary at the
liquid surface at point is impermeable to air, since air is insoluble in benzene liquid.
Hence, air (B) cannot diffuse into or away from the surface. At point 2, the partial
pressure pA2 = 0, since a large volume of air is passing by.
76
 Air (B) Mass Transfer
2 PA2

z0

z2 – z1
z
ZF
NA

1 PA1
Liquid
Benzene (A)

Figure 3.4 : Diffusion of Benzene (A) through Non-diffusing Air (B)

Another example is absorption of NH3 (A) vapour which is in air (B) by water as shown
in Figure 3.5. The water surface is impermeable to the air as air is very slightly soluble in
water. Thus, since B cannot diffuse, NB = 0. B

1 NH3 (A)
air (B)
NA

z2 – z1

Liquid Water

Figure 3.5 : Ammonia in Air being Absorbed into Water

For the species A diffusing through stagnant, non-diffusing species B where NB = 0, B

Eq. (3.44) gives for steady state

dx A c A
N A = − c DAB + ( N A + 0) . . . (3.50)
dz c
p c p
Keeping the total pressure p constant, substituting c = , p A = x A p and A = A
RT c p
into Eq. (3.50)
DAB dp A p
NA = − + A NA . . . (3.51)
RT dz p

Rearranging Eq. (3.51) and integrating we get,

⎛ p ⎞ D dp A
N A ⎜1 − A ⎟ = − AB . . . (3.52)
⎝ p ⎠ RT dz
z2 pA2
DAB dp A
NA ∫ dz = −
RT ∫ p
. . . (3.53)
z1 p A1 1− A
p

DAB p p − p A2
NA = ln . . . (3.54)
RT ( z2 − z1 ) p − p A1

Eq. (3.54) is the final expression to be used to calculate the flux A.

Now, p = p A1 + pB1 = p A2 + pB 2 . . . (3.55)
77
Introduction to Heat Hence, pB1 = p − p A1 . . . (3.56)
and Mass Transfer
And, pB 2 = p − p A2 . . . (3.57)

The log mean part of the inert species B can be written as

pB 2 − pB1 p A1 − p A2
pBM = = . . . (3.58)
⎛p ⎞ ⎛ p − p A2 ⎞
ln ⎜ B 2 ⎟ ln ⎜ ⎟
⎝ pB1 ⎠ ⎝ p − p A1 ⎠
Substituting Eq. (3.58) into Eq. (3.54),
DAB p
NA = ( p A1 − p A2 ) . . . (3.59)
RT ( z2 − z1 ) pBM

Example 3.1
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 0.60 atm and at the other end 0.2 m (20 cm) pA2 = 0.20 atm.
Calculate the flux of He at steady state if DAB of the He-N2 mixture is
0.687 × 10– 4 m2/s (0.687 cm2/s). Use SI and cgs units.
Solution
Since total pressure p is constant, then c is constant, where c is as follows for a gas
from the perfect gas law.
PV = n RT

n P
= =c
V RT
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 cm3 atm/g mol.K.
For steady state the flux J*Az is constant. Also, DAB for a gas is constant. We can
write,
z2 cA2
J ∗Az ∫ dz = − DAB ∫ dc A
z1 c A1

DAB (c A1 − c A2 )
J ∗Az =
z2 − z1

Also, from the perfect gas law, pA V = nA RT, and

p A1 n A
c A1 = =
RT V
DAB ( p A1 − p A2 )
Now, J ∗Az =
RT ( z2 − z1 )

This is the final equation to use, which is in the form easily used for gases. Partial
pressures are pA1 = 0.6 atm = 0.6 × 1.01325 × 105 = 6.08 × 104 Pa and
pA2 = 0.2 atm = 0.2 × 1.01325 × 105 = 2.027 × 104 Pa. then, using SI units,

(0.687 × 10− 4 ) (6.08 × 104 − 2.027 × 104 )

J ∗Az =
8314 (298) (0.20 − 0)

= 5.63 × 10– 6 kg mol A/s. m2

78
 If pressures in atm are used with SI units, Mass Transfer

(0.687 × 10− 4 ) (0.60 − 0.20)

J ∗Az =
(82.06 × 10− 3 ) (298) (0.20 − 0)

= 5.63 × 10– 6 kg mol A/s. m2

For cgs units
0.687 (0.60 − 0.20)
J ∗Az =
82.06 (298) (20 − 0)

= 5.63 × 10– 7 g mol A/s. m2

Example 3.2
Ammonia gas (A) is diffusing through a uniform tube 0.10 m long containing N2
gas (B) at 1.0132 × 105 Pa and 298 K. The diagram is similar to Figure 3.3. At
point 1, pA1 = 1.013 × 104 Pa and at point 2, pA2 = 0.507 × 104 Pa. The diffusivity
DAB = 0.230 × 10– 4 m2/s. Calculate :
(i) The flux J*A at steady state, and
(ii) Repeat for J*B. B

Solution
P = 1.01132 × 105 Pa, z2 – z1 m, and T = 298 K.
Substituting into the following equation

DAB ( p A1 − p A2 ) (0.23 × 10− 4 ) (1.013 × 104 − 0.507 × 104 )

J ∗A = =
RT ( z2 − z1 ) 8314 (298) (0.10 − 0)

= 4.70 × 10– 7 kg mol A/s.m2

For component B

pB1 = P − p A1 = 1.0132 × 105 − 1.013 × 104 = 9.119 × 104 Pa

and pB 2 = P − p A2 = 1.0132 × 105 − 0.507 × 104 = 9.119 × 104 Pa,

DAB ( pB1 − pB 2 ) (0.23 × 10− 4 ) (9.119 × 104 − 9.625 × 104 )

J B∗ = =
RT ( z2 − z1 ) 8314 (298) (0.10 − 0)

= − 4.70 × 10– 7 kg mol B/s.m2

The negative value for J*B means the flux goes from point 2 to 1.
B

Example 3.3
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 × 105 Pa (1.0 atm) and the
temperature is 293 K (20oC). 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 Figure (6.22(a)). Calculate the rate of evaporation at steady in
lb mol/h.ft2 and kg mol/s.m2. The diffusivity of water vapour at 293 K and 1 atm
pressure is 0.250 × 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 suitable conversion factor

DAB = 0.250 × 10− 4 (3.875 × 104 ) = 0.969 ft 2 /h 79

Introduction to Heat 17.54
and Mass Transfer Vapour pressure of water at 20oC is 17.54 mm or p A1 = = 0.0231 atm
760
0.0231 (1.01325 × 105 ) = 2.341 × 103 Pa, pA2 = 0 (pure air). Since the temperature
is 20oC (68oF), T = 460 + 528oR = 293 K.
R = 0.730 ft3 atm/lb mol.oR. To calculate the value of pBM,
pB1 = P − p A1 = 1.00 − 0.0231 = 0.9769 atm
pB 2 = P − p A2 = 1.00 − 0 = 1.00 atm
pB 2 − pB1 1.00 − 0.9769
pBM = = = 0.988 atm = 1.001 × 105
⎛ pB 2 ⎞ ⎛ 1.00 ⎞
ln ⎜ ⎟ ln ⎜ ⎟
⎝ pB1 ⎠ ⎝ 0.9769 ⎠

( pB1 + pB 2 )
Since pB1 is closed to pB2, the linear mean could be used and would
2
be very closed to pBM.
Substituting into Equation with z2 – z1 = 0.5 ft,
DAB P 0.969 (1.0) (0.0231 − 0)
NA = ( p A1 − p A2 ) =
RT ( z2 − z1 ) pBM 0.730 (528) (0.5) (0.988)
= 1.175 × 10– 4 lb mol/h.ft2
(0.250 × 10− 4 ) (1.01325 × 105 ) (2.341 × 103 − 0)
NA =
8314 (293) (0.1524) (1.001 × 105 )
= 1.595 × 10– 7 kg mol/s.m2
Exercise 3.1
(a) A gas of CH4 and He is contained in a tube at 101.32 kPa pressure and
298 K. At one point the partial pressure of methane is pA1 = 60.79 kPa and at
a point 0.02 m distance away, pA2 = 20.26 kPa. If the total pressure is
constant throughout the tube, calculate the flux of CH4 (methane) at steady-
state for equimolar counter-diffusion.
(b) The gas CO2 is diffusing at steady state through a tube 0.20 m long having a
diameter of 0.01 m and containing N2 at 298 K. The total pressure is
constant at 101.32 kPa. The partial pressure of CO2 at one end is 456 mm
Hg and 76 mm Hg at the other end. The diffusivity DAB is 1.67 × 10– 5 m2/s
at 298 K. Calculate the flux of CO2 in cgs and SI units for equimolar
counter-diffusion.

Exercise 3.2
(a) Ammonia gas (A) and nitrogen gas (B) are diffusing in counterdiffusion
through a straight glass tube 2.0 ft (0.610 m) long with an inside diameter of
0.080 ft (24.4 mm) at 298 K and 101.32 kPa. Both ends of the tube are
connected to large mixed chambers at 101.32 kPa. The partial pressure of
NH3 in one chamber is constant at 20.0 kPa and 6.666 kPa in the other
chamber. The diffusivity at 298 K and 101.32 kPa is 2.30 × 10– 5 m2/s.
(i) Calculate the diffusion of NH3 in lb mol/h and kg mol/s.
(ii) Calculate the diffusion of N2.
(iii) Calculate the partial pressures at a point 1.0 ft (0.305 m) in the tube
and plot pA, pB and P versus distance z.
B

80
 (b) Ammonia gas is diffusing through N2 under steady-state conditions with N2 Mass Transfer
non-diffusing since it is insoluble in one boundary. The total pressure is
1.013 × 105 Pa and the temperature is 298 K. The partial pressure of NH3 at
one point is 1.333 × 104 Pa and at the other point 20 mm away it is
6.666 × 103 Pa. The DAB for the mixture at 1.013 × 105 Pa and 298 K is
2.30 × 10– 5 m2/s.
(i) Calculate the flux of NH3 in kg mol/s.m2.
(ii) Do the same as (i) but assume that N2 also diffuses, i.e. both
boundaries are permeable to both gases and the flux is equimolar
counter-diffusion. In which case is the flux greater?
(c) Methane gas is diffusing in a straight tube 0.1 m long containing helium at
298 K and a total pressure of 1.01325 × 105 Pa. The partial pressure of CH4
at one end is 1.400 × 104 Pa and 1.333 × 103 Pa at the other end. Helium is
insoluble in one boundary, and hence is non-diffusing or stagnant. The
diffusivity is given in Table 6.2. Calculate the flux of methane in
kg mol/s.m2 at steady state.

3.11 SUMMARY
Let us summarise what we have learnt in this unit.
Present unit describes the mass transport phenomena. Physical origin and rate equation
for mass transfer are explained in details. Mass transfer may occur due to the molecular
diffusion in a stationary medium due to a concentration gradient. Apart from this, mass
transfer may occur due to the bulk motion of fluid. This is known as convective mass
transfer. Based on the types of mass transfer mechanism, various mass transfer
coefficients may be defined and evaluated. A few special cases of mass transfer between
two species are also described. Some solved examples are given in the unit to clarify the
conceptions. A few unsolved problems are given at the end of the unit, which will help
you to have more insight of the theory.

3.12 KEY WORDS

Fick’s Law : Defines a second important transport property,
namely, the binary diffusion coefficient or mass
diffusivity, DAB.
Diffusional Mass Transfer : Mass transfer in a stationary medium due to the
concentration gradient.
Convective Mass Transfer : Mass transfer due to bulk fluid motion.
Solute : A solid added to a solvent

3.13 ANSWERS TO SAQ’s

Refer the preceding text in this unit for all the Answers to SAQs.

81
Introduction to Heat
and Mass Transfer FURTHER READINGS
F. P. Incropera and D. P. Dewitt (2004), Fundamentals of Heat and Mass Transfer, John
Wiley and Sons, 5th Edition.
W. M. Rohsenow and H. C. Choi (1961), Heat Mass and Momentum Transfer,
Prentice-Hall Englewood Cliffs, N. J.
E. R. G. Eckert and R. M. Drake Jr. (1959), Heat and Mass Transfer, McGraw-Hill,
New York.
P. K. Nag (2002), Heat Transfer, Tata McGraw-Hill Publishing Company Limited,
New Delhi.
P. Ghoshdastidar (2004), Heat Transfer, Oxford University Press.
J. P. Holman (2002), Heat Transfer, Tata McGraw-Hill, New Delhi, 9th Edition.
E. Fried (1969), Thermal Conduction Contribution to Heat Transfer at Contacts,
Thermal Conductivity, R. P. Tye [Ed], Volume 2, Academic Press, London.
R. B. Bird (1956), Advance Chem. Eng., 1, 170.
R. B. Bird, W. E. Stewart, and E. N. Lightfoot (1060), Transport Phenomena, Wiley,
New York.
J. O. Hirschfelder, C. F. Curtiss, and R. B. Bird (1954), Molecular Theory of Gases and
Liquids, Wiley, New York.
R. E. Treybel (1980), Mass Transfer Operations, 3rd Edition, McGraw-Hill Books
Company, New York.
C. J. Geankoplis (2004), Transport Processes and Unit Operations, 3rd Edition,
Prentice-Hall of India Pvt. Ltd, New Delhi.
M. N. Ozisik (1985), Heat Transfer – A Basic Approach, McGraw-Hill Book Company.

82
 Mass Transfer
HEAT AND MASS TRANSFER
This course consists of 6 blocks.
Block 1, Introduction to Heat and Mass Transfer, deals with the basic concepts of heat
and mass transfer and gives a bird’s eye view of the mechanisms. It builds up the
necessary background for the understanding of the physical significances of the
conduction, convection and radiation heat transfer. The phenomena of mass transfer,
mechanism of mass transfer and various types of mass transfer are discussed.
Block 2, Conduction, deals with the governing equations of conduction heat transfer.
Application of Fourier’s law to steady and unsteady state conduction has been analysed.
The governing equation of heat conduction is presented in rectangular, cylindrical as well
as spherical coordinates. Formulation and solution are done for extended surfaces.
Performance parameters such as fin efficiency and effectiveness are discussed in details.
Block 3, Convection, deals with heat transfer by convection and discusses the physical
and mathematical basis for the understanding of convective transport and to reveal
various heat transfer correlations. The analysis of convection is complicated because the
fluid motion is affected by pressure drop, drag force and heat transfer. The literature of
convective heat transfer is overwhelming and ever growing.
Block 4, Radiation, deals with the third mode of heat transfer, i.e. radiation has been
considered. Thermal radiation is that electromagnetic radiation emitted by a body as a
result of its temperature. The principles of radiation, radiation intensity and emissive
power are discussed. Concept of blackbody and laws of radiation are discussed.
Block 5, Mass Transfer, deals with mass transfer processes occur in a variety of
applications in mechanical, chemical and aerospace engineering. Similarly, mass transfer
is also considered in many of the processes in physics, chemistry and biology. Typical
examples include transpiration cooling of jet engines and rocket motors, the ablative
cooling of space vehicles during reentry into the atmosphere, mass transfer from laminar
and turbulent streams onto the surface of a conduit, evaporation and condensation in heat
exchangers, membrane separations, etc.
Molecular diffusion and Ficks law of diffusion are discussed.
Block 6, Heat and Mass Transfer Applications, deals with applications of heat and mass
transfer in practical engineering fields. Different types of heat exchangers utilized in
industries are discussed. The very purpose of the entire course will remain incomplete if
we do not discuss about heat and mass transfer associated with chemical processes.
Chemical processes such as evaporation, liquid-liquid extraction, adsorption and
membrane separation are in use in industry where lot of mass transfer is involved. This
block mainly devoted for applications of heat and mass transfer in chemical processes.

83
Introduction to Heat
and Mass Transfer INTRODUCTION TO HEAT AND MASS
TRANSFER
Unit 1 introduces the basic concepts of heat and mass transfer and gives a bird’s eye view
of the mechanisms. A discussion of units and dimension is also presented. Unit 2 builds
up the necessary background for the understanding of the physical significances of the
conduction, convection and radiation heat transfer. Emphasis is placed on the
mathematical formulation of practical heat conduction problems. This matter is illustrated
with numerous representative examples. Interaction of conduction, convection and
radiation is also discussed. Unit 3 deals with the phenomena of mass transfer. Mechanism
of mass transfer and various types of mass transfer are discussed. The unit is supported
with solved problems for better insight of the mass transfer mechanism. All the three
units include some unsolved problems and SAQs which will help you understanding the
basic heat and mass transfer phenomena.

84