Diffusion Mass

Transfer
 Introduction
 Mass transfer is mass in transit as the result of a species
concentration difference in a mixture.
 Mass is certainly transferred whenever there is;
 Bulk fluid on motion (advection).
 By diffusion for the particle in random molecular
motion.
 The example of mass transfer is;
 The dispersion of oxides of sulfur released from a
power plant smoke stack into the environment.
 The transfer of water vapor into dry air, as in a home
humidifier.
 There are two modes of mass transfer that are;
 Mass transfer by convection, which is analogous to
convection heat transfer and
 Mass transfer by diffusion which can be analogous to
conduction heat transfer.
 6.1. Physical Origins and Rate Equations
6.1.1. Physical Origins
 Consider a chamber in which two different gas
species at the same temperature and pressure
are initially separated by a partition.
 Cont….
 Mass diffusion occurs in liquids and solids, as
well as in gases.
 However, mass transfer is strongly influenced
by molecular spacing.
 Therefore, diffusion occurs more readily in
gases than in liquids and more readily in liquids
than in solids.
6.1.2. Mixture Composition
 A mixture consists of two or more chemical
constituents (species).
 The amount of any species i may be quantified
in terms of;
 Its mass density ρi (kg/m3) or
 Its molar concentration Ci (kmol/m3).
 The mass density and molar concentration are
related through the species molecular weight,
Mi (kg/kmol), such that;
ρi = MiCi ………………………………..6.1
 Cont…
 With ρi representing the mass of species i per unit volume
of the mixture, the mixture mass density is;
ρ= σ 𝜌𝑖..........................................6.2
 Similarly, the total number of moles per unit volume of the
mixture is;
C = σ 𝐶𝑖………………………………………….6.3
 The amount of species i in a mixture may also be quantified
in terms of its mass fraction;
𝜌𝑖
mi = ……………………………………….6.4
𝜌
 Or its mole fraction
𝐶𝑖
xi = = ………………………………………….6.5
𝐶
 Cont…
 From Equations 6.2 and 6.3, it follows that;
σ 𝑚𝑖 = 1 …………….6.6 and σ 𝑥𝑖 = 1………………6.7
 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 𝑃𝑖
ρi = ......................6.8. and Ci = ...........................6.9
𝑅𝑖𝑇 ℛ𝑇
 Where Ri is the gas constant for species i and
 ℛ is the universal gas constant.
 Using Equations 6.5 and 6.9 with Dalton.s law of partial
pressures,
P = σ 𝑃𝑖……………………………………..6.10
 It follows that;
𝑃𝑖 𝐶𝑖
xi = = …………………………………………6.11
𝑃 𝐶
 6.1.3. Fick’s Law of Diffusion
 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;
jA = -ρDAB 𝛻 𝑚𝐴………………………………………..6.12
jA* = -CDAB𝛻xA…………………………………………….6.13
 The quantity jA (kg/sm2) is diffusive mass flux of species
A.
 It is the amount of A that is transferred by
diffusion per unit time and per unit area
perpendicular to the direction of transfer and
 It is proportional to the mixture mass density, ρ= ρ
A+ ρ B (kg/m3), and to the gradient in the species
mass fraction, mA = ρ A/ ρ.
 Cont…
 The species flux may also be evaluated on a
molar basis;
 Where J*A (kmol/s m2) is the diffusive
molar flux of species A.
 It is proportional to the total molar
concentration of the mixture, C = CA + CB
(kmol/m3), and to the gradient in the
species mole fraction, xA = CA/C.
 6.1.4. Mass Diffusivity
 To predicting the mass diffusivity DAB for the
binary mixture of two gases, A and B. Assuming
ideal gas behavior, kinetic theory may be used to
show that;

…………………6.14

Where, c is the mean electron velocity, and 𝜆mfp is

the electron mean free path, which is defined as the
average distance traveled by an electron before it
collides with either an imperfection in the material.
 Cont….
c increases with increasing temperature and
decreasing molecular weight,
 Therefore the mass diffusivity increases with
increasing temperature and decreasing
molecular weight.
 Because of λmfp is inversely proportional to gas
pressure, the mass diffusivity decreases with
increasing pressure.
 Example -1
1. Consider the diffusion of hydrogen (species A) in air, liquid
water, or iron (species B) at T = 293 K. Calculate the species
flux on both molar and mass bases if the concentration
gradient at a particular location is dCA/dx = 1 kmol/m3 . m.
Compare the value of the mass diffusivity to the thermal
diffusivity. The mole fraction of the hydrogen, xA, is much less
than unity.
Cont…
Determining Mass Fractions from Mole Fractions
2. The composition of dry standard atmosphere is given on
a molar basis to be 78.1 percent N2, 20.9 percent O2, and
1.0 percent Ar and small amounts of other constituents
(Fig. below). Treating other constituents as Ar, determine
the mass fractions of the constituents of air.
 6.2. Mass Transfer in Nonstationary Media
6.2.1. Absolute and Diffusive Species Fluxes
 The diffusion of a species always involves the movement
of molecules or atoms from one location to another.
 The molecular scale motion results in bulk motion.
 To obtain an expression for the absolute mass flux,
consider species A in a binary mixture of A and B. The
absolute mass flux n’’A is related to the species absolute
velocity vA by;
n’’A = ρAvA………………………………..6.15
 A value of vA associated with any point in the
mixture, and
 It is interpreted as the average velocity of all A
particles in a small volume element.
 Cont…
 An average, or aggregate, velocity associated
with the particles of species B, in which case
n’’B = ρBvB……………………………..…6.16
 A mass-average velocity for the mixture may
then be obtained from the requirement that;
ρv = n’’ = n’’A + n’’B = ρAvA + ρBvB……..6.17
and Giving
v = mAvA + mBvB…………………….6.18
 Cont….
 The absolute flux of any species A will be equal to the
sum of the flux due to;
 Molecular diffusion and
 Bulk motion
Where,
 Absolute flux (n’’A)= ρAvA
 Diffusion flux (jA)= m/A
 Flux due to bulk motion = ρAv
 Therefore, ρAvA = m/A + ρAv or
Diffusion flux= m/A = ρA(vA – v)
 So, The mass flux of species A relative to the mixture
mass-average velocity as;
jA = ρA(vA - v)……………………………………….…6.19
 Cont…
 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
Equations 6.15 and 6.19 that;
n’’A = jA +ρAv……………………………………6.20
 This expression delineates the 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 advection (i.e., due to
motion of A with the mass average motion of the
mixture).
 Cont….
 Substituting from Equations 6.12 and 6.17, we obtain;

………………….6.21
 If the second term on the right-hand side of
Equation 6.21 is zero, mass transfer of species A
occurs purely by diffusion.
 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 = ρB(vB - v)………………………6.22
Where, jB = -ρDBA𝛻mB…………………….6.23
 Cont….
 It follows from Equations 6.17, 6.19, and 6.22 that the
diffusive fluxes in a binary mixture are related by;
jA + jB = 0…………………………………………..6.24
 If Equations 6.12 and 6.23 are substituted into
Equation 6.24, and it is recognized that;
 𝛻mA = -𝛻mB,

 since mA + mB = 1

 For a binary mixture, it follows that;

DBA = DAB………………………………………..6.25
Cont….
 Hence, as in Equation 6.21, the absolute flux of
species B may be expressed as;
……………………………….6.26

 The absolute molar fluxes of species A and B may be

expressed as;
N’’A = CAvA and N’’B = CBvB……..6.27
 A molar-average velocity for the mixture, v*, is
obtained from the requirement that;
N’’ = N’’A + N’’B = Cv* = CAvA + CBvB…………6.28
Giving
v* = xAvA + xBvB………………………………..6.29
Cont….
 Equation 6.27 provides the absolute molar flux of
species A and B.
 The molar flux of A relative to the mixture molar
average velocity J*A, termed the diffusive flux,
obtained from Equation 6.13 or from the expression;
J*A = CA(vA - v*)………………………6.30
 To determine an expression similar in form to
Equation 6.21, we combine Equations 6.27 and 6.30 to
obtain;
N’’A = J*A + CA v*……………………6.31
Or, from Equations 6.13 and 6.28,
………………6.32
Cont….
 Note that Equation 6.32 represents the absolute
molar flux as the sum of a diffusive flux and an
advective flux.
 Again, if the second term on the right-hand side is
zero, mass transfer is purely by diffusion and is
analogous to heat conduction, when formulated in
molar quantities instead of mass quantities.
 For the binary mixture, it also follows that;
J*A + J*B = 0………………………6.33
 Example -2
1. Water vapor and air are passing through a 2 m long steel
pipe (radius is 25 cm). The molar fraction of water vapor is
give as 0.37.
The physical properties of the two gases are given:
At 25℃ density of water is 997 kg/m³ and density of air is 1.1839
kg/m³.Molecular weights are 28.9647 kg/kmol and 18 kg/kmol
for air and water respectively. What will be the absolute mass
rate and mole rate of the mixture if the mass-average velocity
of air is 2 m/s and water vapor is 1.5 m/s.(assume non-binary
diffusion).
 Cont…
2. Pressurized hydrogen gas is stored at 358 K in a 4.8-m-outer-
diameter spherical container made of nickel (Fig. below. The
shell of the container is 6 cm thick. The molar concentration of
hydrogen in the nickel at the inner surface is determined to be
0.087 kmol/m3. The concentration of hydrogen in the nickel at
the outer surface is negligible. Determine the mass flow rate of
hydrogen by diffusion through the nickel container.
 6.3. Conservation of Species for a
Stationary Medium
6.3.1. Conservation of Species for a
Control Volume
 The law of conservation of species plays an
important role in the analysis of mass transfer
problems.
The rate at which the
The rate at which the The rate at which this
species mass is
mass species enters + generated within the
- species mass leaves
to a control volume, the control volume
control volume

The rate of increase

= of the species mass
stored within the
control volume.
Cont….
 For any species A may enter and leave the
control volume due to both fluid motion and
diffusion across the control surface.
 The conservation equation may then be
expressed on a rate basis as;
……………6.41

 Species generation exists when chemical

reactions occur in the system.
 6.3.2. The Mass Diffusion Equation
 Mass, or species, diffusion equation that is
analogous to the heat equation.
 We consider a medium that is a binary mixture of
species A and B for which the stationary medium
approximation holds.
 That is, mass transfer may be approximated as
occurring only by diffusion because advection is
negligible.
 The resulting equation could be solved for the
species concentration distribution, which could be
used with Fick’s law to determine the species
diffusion rate at any point in the medium
 Cont…
 Allowing for concentration gradients in each of the x, y,
and z coordinate directions, we first define a differential
control volume, dx dy dz, within the medium.
 The concentration gradients, diffusion must result in the
transport of species A through the control surfaces.

………6.42a
 Cont….

Differential
control volume,
dx dy dz, for
species diffusion
analysis in
Cartesian
coordinates.

…………….. 6.42b

………………6.42c
 Cont…
 The rate at which species A is generated within
the control volume due to such reactions may
be expressed as;
………………….6.43
Where nA is the rate of increase of the mass of species A
per unit volume of the mixture (kg/s m3).
 The mass of species A stored within the control
volume, and the rate of change is;

………………………………6.44
 Cont….
 With mass inflow rates determined by n’’A,x, n’’A,y, and
n’’A,z and the outflow rates determined by Equations
6.42, Equations 6.42 through 6.44 may be substituted
into Equation 6.41 to obtain;

………………………6.45
 Then, substituting the x, y, and z components of
Equation n’’A = jA = 𝜌DAB𝛻mA (stationary medium
approximation is appropriate, the diffusive mass and
molar fluxes), we obtain;

……6.46a
Cont…
 In terms of the molar concentration, a similar
derivation yields;
…6.47a

 In particular, if DAB and ρ are constant,

Equation 14.46a may be expressed as;

……………..6.46b
 Cont…
 Similarly, if DAB and C are constant, Equation
6.47a may be expressed as;
……………………6.47b

 The species diffusion equations may also be expressed

in cylindrical and spherical coordinates.
 These alternative forms can be inferred from the
analogous expressions for heat transfer, equation and
in terms of the molar concentration are:
Cont…
 Cylindrical Coordinates:

 Spherical Coordinates:
 Example -3
1. The efficacy of pharmaceutical products is reduced by
prolonged exposure to high temperature, light, and humidity.
For water vapor–sensitive consumer products that are in tablet
or capsule form, and might be stored in humid environments
such as bathroom medicine cabinets, blister packaging is used
to limit the direct exposure of the medicine to humid conditions
until immediately before its ingestion. Consider tablets that are
contained in a blister package composed of a flat lidding sheet
and a second, formed sheet that includes troughs to hold each
tablet. The formed sheet is L =50𝜇m thick and is fabricated of a
polymer material. Each trough is of diameter D = 5 mm and
depth h = 3 mm.
The lidding sheet is fabricated of aluminum foil. The binary
diffusion coefficient for water vapor in the polymer is DAB = 6 x
10−14 m2/s while the aluminum may be assumed to be impermeable
to water vapor. For molar concentrations of water vapor in the
polymer at the outer and inner surfaces of CA,s1 = 4.5 x
10−3 kmol/m3 and CA,s2 = 0.5 x 10−3 kmol/m3, respectively.
 Cont…
 Determine the rate at which water vapor is transferred
through the trough wall to the tablet.