Mass Transfer with

UNIT 13 MASS TRANSFER WITH TRANSIENT Transient Diffusion and

Chemical Reaction
DIFFUSION AND CHEMICAL
REACTION
Structure
13.1 Introduction
Objectives
13.2 Examples of Unsteady Mass Transfer Problems
13.3 General Transient Diffusion : No Reaction or Internal Convection
13.4 Unsteady State Three-dimensional Mass Diffusion in Stationary Media
13.4.1 Derivation of Basic Equation
13.4.2 Diffusion in a Flat Plate with Negligible Surface Resistance
13.4.3 Unsteady-state Diffusion in Various Geometries
13.5 Equation of Continuity for a Binary Mixture
13.6 Special Cases of the Equation of Continuity
13.6.1 Equations for Constants c and DAB
13.6.2 Equimolar Counterdiffusion for Gases
13.6.3 Special Cases of the General Diffusion Equation at Steady State
13.7 Unsteady State Diffusion and Reaction in a Semi-infinite Medium
13.8 Numerical Methods for Unsteady State Molecular Diffusion
13.8.1 Unsteady State Numerical Method for Diffusion
13.8.2 Boundary Conditions for Numerical Method for a Slab
13.9 Mass Diffusion with Homogeneous Chemical Reactions
13.10 Summary
13.11 Key Words
13.12 Answers to SAQs

13.1 INTRODUCTION
Present unit deals with mass transfer with chemical reaction and transient diffusion. As
discussed in Unit 12, steady state mass transfer means that the concentration variables
and the rate of mass transfer are independent of time. Many systems of importance
operate under conditions of steady state behavoiur. Other systems exhibit transient (time
dependent behavoiur), and the time dependence may be the key issue in developing a
mathematical model of the system. Another important aspect is mass transfer with
chemical reactions. In the present unit a brief discussion on the same is presented.
Objectives
After studying this unit, you should be able to
• interprete the importance of unsteady state mass diffusion phenomena,
• derive transient diffusion equation for various conditions and geometries,
• apply numerical methods in solving transient mass transfer problems, and
• understand chemical reaction associated with mass transfer. 45
Mass Transfer
13.2 EXAMPLES OF UNSTEADY STATE MASS TRANSFER
PROBLEMS
Unsteady Mass Diffusion Across a Membrane
A membrane test cell consists of two compartments separated by a polymeric
membrane. In this example, we suppose that the membrane is permeable to olefin
vapours, like ethylene, but impermeable to aliphatic hydrocarbon vapours. The top
compartment is initially evacuated, but the lower one is filled with ethylene gas.
We measure the ethylene concentration subsequently appearing in the vapour in
the top compartment as a function of time.
Dissolving Particle
The dissolution of a particle is often controlled by diffusion into the surrounding
liquid. A transient analysis can tell us how much time is required to reach a steady
rate of dissolution, following some initial transient period. In addition, we can find
the time for the particle to “disappear” through dissolution.
Evaporation of Solvent from a Film
Polymer coating are often applied from solution, and it is necessary to dry the
resulting film by promoting the evaporation of solvent. Because diffusion is
relatively slow within viscous polymeric matrix, evaporation is controlled by the
diffusion process within the film.
Stroke and Cell Death
Capillaries supply oxygen to the tissue, and diffusion through the tissue zone is
rate limiting. If blood flow is stopped, cell respiration depletes the dissolved
oxygen content until the oxygen level is too low to support the cell function. A
transient analysis can indicate how long a cell region will remain viable under
these conditions.
Doping of a Semiconductor Film
To control the conductivity of a silicon film of a semiconductor device, very small
amounts of a specific atom, such as boron, are caused to diffuse into the region
near the surface of the solid film. This transient process, called doping, is central to
control of the electronic properties of a device. Careful control of the concentration
profile of the dopant (e.g. boron atoms) is achieved through an understanding of
transient diffusion in the solid.

13.3 GENERAL TRANSIENT DIFFUSION : NO REACTION

OR INTERNAL CONVECTION
The general mass diffusion equation in some domain V is given by
∂C A
= DAB ∇ 2 C A . . . (13.1)
∂t
The form of Laplacian operator (∇2) depends on the coordinate system. Table 13.1 gives
these forms for planar, cylindrical and spherical coordinates. In absence of convection,
there is no velocity term on the left hand side of the diffusion equation.
Table 13.1 : The Laplacian Operator ∇2
2 2 2
2 ∂ ∂ ∂
Cartesian Coordinate ∇ = + +
2 2 2
∂x ∂y ∂z
2 2
2 1 ∂ ⎛ ∂ ⎞ 1 ∂ ∂
Cylindrical Coordinate ∇ = ⎜r ⎟+ +
r ∂r ⎝ ∂r ⎠
2
r ∂θ
2
∂z
2

2
2 1 ∂ ⎛ 2 ∂ ⎞ 1 ⎛ ∂ ⎞ 1 ∂
Spherical Coordinate ∇ = 2 ⎜r ⎟+ ⎜ sin θ ⎟ +
r ∂r ⎝ ∂r ⎠ r sin θ ⎝
2
∂θ ⎠
2 2
r sin θ ∂φ
2
46
An initial condition is required, which we write as Mass Transfer with
Transient Diffusion and
C A = C A0 ( r , 0) . . . (13.2) Chemical Reaction

at t≤0
While the initial state of the system may be spatially uniform, rendering C as a function
of the vector position r, we will almost always consider simple problems here, where the
initial concentration distribution is spatially uniform. Boundary conditions can take any
of a number of forms depending on the physics of the problem.

13.4 UNSTEADY STATE THREE-DIMENSIONAL MASS

DIFFUSION IN STATIONARY MEDIA
13.4.1 Derivation of Basic Equation
In Units 11 and 12 we considered various mass-transfer systems where the concentration
or partial pressure at any point and the diffusion flux were constant with time, hence at
steady state. Before steady state can be reached, time must elapse after the mass-transfer
process is initiated for the unsteady-state conditions to disappear.
For unsteady-state molecular diffusion without generation
∂Γ ∂ 2Γ
=δ 2 . . . (13.3)
∂t ∂z
Eq. (13.3) is similar to the unsteady-state equation for heat conduction given by
∂T ∂ 2T
=α 2 . . . (13.4)
∂t ∂x
The derivation of the unsteady-state diffusion equation in one direction for mass transfer
is also similar to that done for heat transfer equation. We refer to Figure 13.1 where mass
is diffusing in the x-direction in a cube composed of a solid, stagnant gas, or stagnant
liquid and having dimensions Δx, Δy and Δz. For diffusion in the x-direction we write
∂c A
N Ax = − DAB . . . (13.5)
∂x
∂c A
The term means the partial of CA with respect to x or the rate of change of CA with x
∂x
when the other variable time t is kept constant. Next we make a mass balance on
component A in terms of moles for no generation.
Rate of input = Rate of output + Rate of accumulation . . . (13.6)

Rate of Input Rate of Output

NA x x NA x x+Δx
Δy

Δz
x
Δx x + Δx

Figure 13.1 : Unsteady-state Difusión in One-direction

The rate of input and rate of output in kg mol A/s are

∂c A
Rate of input = N Ax = − DAB . . . (13.7)
x
∂x x
47
Mass Transfer ∂c A
Rate of output = N Ax = − DAB . . . (13.8)
x+Δ x
∂x x+Δ x

The rate of accumulation is as follows for the volume Δx Δy Δz m3

∂c A
Rate of accumulation = (Δx Δy Δz ) . . . (13.9)
∂t
Substituting Eqs. (13.7), (13.8), and (13.9) into Eq. (13.6) and dividing by Δx Δy Δz ,

∂c A ∂c A
−
∂x x ∂x x + Δx ∂c A
− DAB = . . . (13.10)
Δx ∂t
Letting Δx approach zero,

∂c A ∂ 2cA
= DAB . . . (13.11)
∂t ∂x 2
The above holds for a constant diffusivity DAB. If DAB is a variable,

⎛ D ∂c ⎞
∂ ⎜ AB A ⎟
∂c A ∂x ⎠
= ⎝ . . . (13.12)
∂t ∂x
Eq. (13.11) relates the concentration CA with position x and time t. For diffusion in all
three directions a similar derivation gives

∂c A ⎛ ∂ 2cA ∂ 2cA ∂ 2cA ⎞

= DAB ⎜⎜ 2 + + ⎟ . . . (13.13)
∂t ⎝ ∂x ∂y 2 ∂z 2 ⎠⎟

In the remainder of this section, the solutions of Eqs. (13.11) and (13.13) will be
considered. Note the mathematical similarity between the equations for heat conduction,

∂T ∂ 2T
=α 2 . . . (13.14)
∂t ∂x
and Eq. (13.11) for diffusion. Because of this similarity, the mathematical methods used
for solution of the unsteady-state heat-conduction equation can be used for unsteady-state
mass transfer.
13.4.2 Diffusion in a Flat Plate with Negligible Surface Resistance
To illustrate an analytical method of solving Eq. (13.11), we will derive the solution for
unsteady-state diffusion in the x direction for a plate of thickness 2x1, as shown in
Figure 13.2. For diffusion in one direction,

∂c A ∂ 2cA
= DAB . . . (13.15)
∂t ∂x 2
Dropping the subscripts A and B for convenience,

∂c ∂ 2c
=D 2 . . . (13.16)
∂t ∂x
The initial profile of the concentration in the plate at t = 0 is uniform at c = c0 at all x
values, as shown in Figure 13.2. At time t = 0 the concentration of the fluid in the
environment outside is suddenly changed to c1. For a very high mass-transfer coefficient
at the surface will be equal to that in the fluid, which is c1.
48
The initial and boundary conditions are Mass Transfer with
Transient Diffusion and
c1 − c0 Chemical Reaction
c = c0, t = 0, x = x, Y = =1 . . . (13.17)
c1 − c0

c1 − c1
c = c`1, t = t, x = 0, Y = =0
c1 − c0

c1 − c1
c = c`1, t = t, x = 2x1, Y = =0
c1 − c0

Redefining the concentration so it goes between 0 and 1,

c1 − c
Y = . . . (13.18)
c1 − c0

∂Y ∂ 2Y
=D 2 . . . (13.19)
∂t ∂x
c

c at t = t

c0 at t = 0
c1

c1 c1

x
0 x1 2x1

Figure 13.2 : Unsteady-state Diffusion in a Flat Plate with Negligible Surface Resistance

The solution of Eq. (13.19) is an infinite Fourier series and is identical to the solution of
Eq. (13.14) for heat transfer.

c1 − c 4 ⎡1 ⎛ 12 π2 X ⎞ 1π x 1 ⎛ 32 π2 X ⎞ 3π x
Y = = ⎢ exp ⎜ − ⎟ sin + exp ⎜ − ⎟⎟ sin
c1 − c0 π ⎢⎣1 ⎜ 4 ⎠ ⎟ 2 x1 3 ⎜ 4 ⎠ 2 x1
⎝ ⎝

1 ⎛ 52 π 2 X ⎞ 5π x ⎤
+ exp ⎜ − ⎟⎟ sin + . . .⎥ . . . (13.20)
⎜
5 ⎝ 4 ⎠ 2 x1 ⎦⎥

Dt
where, X = , dimensionless
x12

c = concentration at point x and time t in slab

(c1 − c)
Y = = fraction of unaccomplished change, dimensionless
(c1 − c0 )

(c − c0 )
1−Y = = fraction of change.
(c1 − c0 )

Solution of equations similar to Eq. (13.20) are time consuming; convenient charts for
various geometries are available and will be discussed in the next section.
49
Mass Transfer 13.4.3 Unsteady-State Diffusion in Various Geometries
Convection and Boundary Conditions at the Surface
In Figure 13.2 there was no convective resistance at the surface. However, in many
cases when a fluid is outside the solid, convective mass transfer is occurring at the
surface. A convective mass-transfer coefficient kc, similar to a convective
heat-transfer coefficient, is defined as follows :
N A = kc (cL1 − cLi ) . . . (13.21)
where kc is a mass-transfer coefficient in m/s, cL1 is the bulk fluid concentration in
kg mol A/m3, and cLi is the concentration in the fluid just adjacent to the surface of
the solid.
In Figure 13.3(a) the case for a mass-transfer coefficient being present at the
boundary is shown. The concentration drop across the fluid is cL1 − cLi . The
concentration in the solid ci at the surface is in equilibrium with cLi.

cL1 cL1

ci
kc cLi
cLi
kc

ci

NA NA

(a) (b)

cL1 cL1 cLi

ci
kc ci
cLi k c= α

NA NA

(c) (d)
Figure 13.3 : Interface Conditions for Convective Mass Transfer and an Equilibrium Distribution
c
Coefficient K = Li , (a) K = 1, (b) K > 1, (c) K < 1, (d) K > 1 and kc = ∞
ci

In Figure 13.3(a) the concentration cLi in the liquid adjacent to the solid and ci in
the solid at the surface are in equilibrium and also equal. However, unlike heat
transfer, where the temperatures are equal, the concentrations are in equilibrium
and are related by
cLi
K= . . . (13.22)
ci
where K is the equilibrium distribution coefficient (similar to Henry’s law
coefficient for a gas and liquid). The value of K in Figure 13.3(a) is 1.0.
In Figure 13.3(b) the distribution coefficient K is > 1 and cLi > ci, even through
they are in equilibrium. Other cases are shown in Figures 13.3(c) and (d).
Relationship between Mass and Heat-Transfer Parameters
In order to use the unsteady-state heat-conduction charts in Unit 5 for solving
unsteady-state diffusion problems, the dimensionless variables or parameters for
heat transfer must be related to those for mass transfer. In Annexure I the relations
between these variables are tabulated. For K ≠ 1.0, whenever kc appears, it is given
c
as Kkc, and whenever c1 appears, it is given as 1 .
K
50
Unsteady-State Diffusion in more than One Direction Mass Transfer with
Transient Diffusion and
One-dimensional solutions for unsteady-state heat conduction can be extended for Chemical Reaction
multi-dimensional problems. The same method can be used for unsteady-state
diffusion in more than one direction. In a rectangular block in the x, y, and z
directions,
c1
K − cx, y , z
Yx, y , z = (Yx ) (Yy ) (Yz ) = . . . (13.23)
c1
K − c0

where cx, y, z is the concentration at the point x, y, z from the center of the block.
The change in mass flow along x-direction is given by

⎡∂ ⎛ ma ⎞ ⎤
−⎢ ⎜ A ⎟ . δx ⎥ . (δy . δz ) . . . (13.24)
⎣ ∂x ⎝ ⎠x ⎦
Similarly, along y and z-directions, the mass flow changes are given by

⎡ ∂ ⎛m ⎞ ⎤
− ⎢ ⎜ a ⎟ . δy ⎥ . (δx . δz ) . . . (13.25)
⎢⎣ ∂y ⎝ A ⎠ y ⎥⎦

⎡ ∂ ⎛m ⎞ ⎤
and − ⎢ ⎜ a ⎟ . δz ⎥ . (δx . δy ) . . . (13.26)
⎣ ∂z ⎝ A ⎠ z ⎦
The rate of production of species ‘a’ in the control volume is
Qa′′′ . δx . δy . δz . . . (13.27)

where Qa′′′ is the rate of production of species ‘a’ per m3.

The rate of change of concentration of ‘a’ with time within the control volume is
given as
∂Ca
. (δx . δy . δz ) . . . (13.28)
∂t
For the mass balance, the required condition is
∂Ca ∂ ⎛ ma ⎞ ∂ ⎛ ma ⎞ ∂ ⎛ ma ⎞
=− − − + Qa′′′
∂x ⎝ A ⎠ x ∂y ⎝ A ⎠ y ∂z ⎜⎝ A ⎟⎠ z
⎜ ⎟ ⎜ ⎟ . . . (13.29)
∂t

For isotropic medium, the diffusion coefficient D is same in all three directions.
Then the above equation can be written as

∂Ca ∂ ⎛ ∂Ca ⎞ ∂ ⎛ ∂Ca ⎞ ∂ ⎛ ∂Ca ⎞

=− − ⎜D ⎟− + Qa′′′
∂x ⎝⎜ ∂x ⎠⎟ ∂y ⎝ ∂y ⎠ ∂z ⎝⎜ ∂z ⎠⎟
D . . . (13.30)
∂t

If D is constant and if Qa′′′ = 0 , then

⎡ ∂ 2C ∂ 2Ca ∂ 2Ca ⎤ ∂Ca

D ⎢ 2a + + ⎥= . . . (13.31)
⎣⎢ ∂x ∂y 2 ∂z 2 ⎦⎥ ∂t

A few boundary conditions for solving the above equations are listed below :
(a) Specified boundary condition
Ca = Ca 0 at x = 0
51
Mass Transfer (b) Impermeable boundary
∂Ca
= 0 at x = 0
∂x
(c) Given mass flux at the boundary
∂Ca 1 ⎛m ⎞
= − ⎜ a ⎟ at x = 0
∂x D⎝ A ⎠
hm
=− (Cao − Ca∞ )
D
where hm is mass transfer coefficient.
SAQ 1
(a) What do you mean by transient mass diffusion?
(b) Give a few examples of transient mass diffusion
(c) Write down the general transient diffusion equation for 1-D for no chemical
reaction and internal convection. How do you extend the same for
multi-dimensional cases?
(d) Derive the transient mass diffusion expression for a diffusion over a flat plat
with negligible surface resistance. What are the initial and boundary
conditions?

13.5 EQUATION OF CONTINUITY FOR A BINARY

MIXTURE
A general equation can be derived for a binary mixture of A and B for diffusion and
convection that also includes the terms for unsteady-state diffusion and chemical
reaction. We shall make a mass balance on component A on an element Δx Δy Δz fixed in
space as shown in Figure 13.4. The general mass balance on A is
(Rate of mass A in) – (Rate of mass A out) + (Rate of generation of mass A)
= Rate of accumulation of mass A) . . . (13.32)
The rate of mass A entering in the direction relative to stationary coordinates is
(n Ax x ) Δy Δz kg A/s and leaving is (nAx x + Δx ) Δy Δz . Similar terms can be written for
the y and z directions. The rate of chemical production of A generated/s . m3 volume and
the total gas generated is rA ( Δx Δy Δz) kg A/s. The rate of accumulation of A is
⎛ ∂ρ A ⎞
⎜ ∂ ⎟ Δx Δy Δz . Substituting into Eq. (13.32) and letting Δx, Δy and Δz is approach
⎝ t ⎠
zero,

∂ρ A ⎛ ∂n Ax ∂n Ay ∂n Az ⎞
+⎜ + + ⎟ = rA . . . (13.33)
∂t ⎝ ∂x ∂y ∂z ⎠

In vector notation,

52
 ∂ρ A Mass Transfer with
+ (∇ . n A ) = rA . . . (13.34) Transient Diffusion and
∂t Chemical Reaction
Dividing both sides of Eq. (13.33) by MA,

∂c A ⎛ ∂N Ax ∂N Ay ∂N Az ⎞
+⎜ + + ⎟ = RA . . . (13.35)
∂t ⎝ ∂x ∂y ∂z ⎠
z

Δy

nA x x
ηA,x x + Δx
Δz
y

Δx

Figure 13.4 : Mass Balance for A in a Binary Mixture

where RA is kg mol A generated/s.m3.
dx A
Now, N A = − cDAB + c A vM . . . (13.36)
dz
and writing the equation for all three directions, Eq. (13.35) becomes
∂c A
+ (∇ . c A ν M ) − (∇ . cDAB ∇x A ) = RA . . . (13.37)
∂t
This is the final general equation.

13.6 SPECIAL CASES OF THE EQUATION OF

CONTINUITY
13.6.1 Equation for Constant c and DAB
P
In diffusion with gases the total pressure P is often constant. Then, since c = , c is
RT
constant for constant temperature T. Starting with the general Eq. (13.37) and substituting
∇c A
∇x A = , we obtain
c
∂c A
+ c A (∇ . ν M ) + (ν M . ∇c A ) − DAB ∇ 2 c A = RA . . . (13.38)
∂t
13.6.2 Equimolar Counterdiffusion for Gases
For the special case of equimolar counterdiffusion of gases at constant pressure and no
reaction, c = constant, vM = 0, DAB = constant, RA = 0, and Eq. (13.37) becomes
∂c A ⎛ ∂ 2cA ∂ 2cA ∂ 2cA ⎞
= DAB ⎜⎜ 2 + + ⎟ . . . (13.39)
∂t ⎝ ∂x ∂y 2 ∂z 2 ⎠⎟
This equation is Eq. (13.13) derived previously and this equation is also used for
unsteady-state diffusion of a dilute solute A in a solid or a liquid when DAB is constant.
Equation for constant ρ and DAB (liquids). In dilute liquid solutions the mass density ρ
and DAB can often be considered constant. Starting with Eq. (13.34) we substitute
n A = − ρ DAB ∇wA + ρ Aν from Table 7.5 into this equation. Then using the fact that for

53
Mass Transfer ∇ρ A
constant ρ, ∇wA = and also that (∇ . ν ) = 0 , substituting these into the resulting
ρ
equation, and dividing both sides by MA, we obtain
∂c A
+ (ν . ∇c A ) − DAB ∇ 2 c A = RA . . . (13.40)
∂t
13.6.3 Special Cases of the General Diffusion Equation at Steady State
Introduction and Physical Conditions at the Boundaries
The general equation for diffusion and convection of a binary mixture in one
direction with no chemical reaction has been given previously.
dx A c A
N A = − cDAB + (N A + NB ) . . . (13.41)
dz c
To integrate this equation at steady state it is necessary to specify the boundary
conditions at z1 and at z2. Often in many mass transfer problems the molar ratio
NA
is determined by the physical conditions occurring at the two boundaries.
NB

As an example, one boundary of the diffusion path may be impermeable to species

B because B is insoluble in the phase at this boundary. Diffusion of ammonia (A)
and nitrogen (B) through a gas phase to a water phase at the boundary is such a
case since nitrogen is essentially insoluble in water. Hence, NB = 0, since at steady
B

state NB must have the same value at all points in the path of z2 – z1. In some cases,
B

a heat balance in the adjacent phase at the boundary can determine the flux ratios.
For example, if component A condenses at a boundary and releases its latent heat
to component B, which vaporizes and diffuses back, the ratios of the latent heats
determine the flux ratio.
In another example, the boundary concentration can be fixed by having a large
volume of a phase flowing rapidly by with a given concentration xA1. In some cases
the concentration xA1 may be set by an equilibrium condition, whereby xA1 is in
equilibrium with some fixed composition at the boundary. Chemical reactions can
also influence the rates of diffusion and the boundary conditions.
Equimolar Counterdiffusion
For the special case of equimolar counterdiffusion where NA = − NB, B

dx A DAB (c A1 − c A2 )
N A = J ∗A = − cDAB = . . . (13.42)
dz z2 − z1

Diffusion of Gas A Through Stagnant, Non-diffusing Gas B

For gas A diffusing through stagnant non-diffusing gas B, NB = 0B

DAB P
NA = ( p A1 − p A2 ) . . . (13.43)
RT ( z2 − z1 ) pBM

Diffusion and Chemical Reaction at a Boundary

Often in catalytic reactions where A and B are diffusing to and from a catalyst
surface, the relation between the fluxes NA and NB at steady state is controlled by
B

the stoichiometry of a reaction at a boundary. An example is gas A diffusing from

the bulk gas phase to the catalyst surface, where it reacts instantaneously and
irreversibly in a heterogeneous reaction as follows :
A → 2B . . . (13.44)

Gas B then diffuses back, as shown in Figure 13.5.

54
At steady state 1 mol of A diffuses to the catalyst for every 2 mol of B diffusing Mass Transfer with
away, or NB = – NA. The negative sign indicates that the fluxes are in opposite
B
Transient Diffusion and
Chemical Reaction
directions. In terms of mole fractions,
dx A
N A = − cDAB + xA ( N A + N B ) . . . (13.45)
dz
Next, substituting NB = − 2 NA into Eq. (13.45),
B

dx A
N A = − cDAB + xA ( N A − 2 N A ) . . . (13.46)
dz
Rearranging and integrating with constant c (P = constant), we obtain the
following :
Instantaneous Surface Reaction
z2 = δ xA2
dx A
NA ∫ dz = − cDAB ∫ 1 + xA
. . . (13.47)
z1 = 0 x A1

cDAB 1 + x A1
NA = ln . . . (13.48)
δ 1 + x A2
Since the reaction is instantaneous, xA2 = 0, because no A can exist next to
the catalyst surface. Eq. (13.48) describes the overall rate of the process of
diffusion plus instantaneous chemical reaction.
Catalyst Surface

NA

NB

Z
Z1 Z2

Figure 13.5 : Diffusion of A and Heterogeneous Reaction at a Surface

Slow Surface Reaction

If the heterogeneous reaction at the surface is not instantaneous but slow for
the reaction A → 2 B , and the reaction is first order,
N Az = δ = k1′ c A = k1′ c x A . . . (13.49)

where k1′ is the first-order heterogeneous reaction velocity constant in m/s.

Eq. (13.48) still holds for this case, but the boundary condition xA2 at z = δ is
obtained by solving for xA in Eq. (13.49),
N Az = δ NA
x A = x A2 = = . . . (13.50)
k1′ c k1′ c

For steady state, N Az = δ = N A . Substituting Eq. (13.49) into Eq. (13.47),

cDAB 1 + x A1
NA = ln . . . (13.51)
δ 1 + NA
k1′ c

55
Mass Transfer The rate in Eq. (13.51) is less than in Eq. (13.48), since the denominator in
1 + NA
the latter equation is 1 + x A2 = 1 + 0 and in the former is .
k1′ c
Diffusion and Homogeneous Reaction in a Phase
Eq. (13.48) was derived for the case of chemical reaction of A at the boundary on a
catalyst surface. In some cases component A undergoes an irreversible chemical
reaction in the homogeneous phase B while diffusing as follows, A → C . Assume
that component A is very dilute in phase B, which can be a gas or a liquid. Then at
steady state the equation for diffusion of A is as follows where the bulk-flow term
is dropped.
dc A
N Az = − DAB +0 . . . (13.52)
dz
Writing a material balance on A shown in Figure 13.6 for the Δz element for steady
state,
(Rate of A in) + (Rate of generation of A)
= (Rate of A out) + (Rate of accumulation of A) . . . (13.53)

N Az z N Az z+Δz
in out

Δz

1 z 2

Figure 13.6 : Homogeneous Chemical Reaction and Diffusion in a Fluid

The first-order reaction rate of A per m3 volume is

Rate of reaction = − k ′ c A . . . (13.54)

where k′ is the reaction velocity constant in s– 1. Substituting into Eq. (13.53) for a
cross-sectional area of 1 m2 with the rate of accumulation being 0 at steady state,
N Az z (1) − k ′ c A (1) (Δz ) = N Az z + Δz (1) + 0 . . . (13.55)

Next we divide through by Δz and let Δz approach zero.

dN Az
− = k ′ cA . . . (13.56)
dz
Substituting Eq. (13.52) into Eq. (13.56),

d 2c A k′
2
= cA . . . (13.57)
dz DAB

The boundary conditions are cA = cA1 for z = 0 and cA – cA2 for z = L. Solving,

56
 ⎛ k′ ⎞ ⎡ k′ ⎤ Mass Transfer with
c A2 sinh ⎜⎜ z ⎟⎟ + c A1 sinh ⎢ (L − z)⎥ Transient Diffusion and

cA = ⎝ DAB ⎠ ⎣ DAB ⎦ . . . (13.58)

Chemical Reaction
⎛ k′ ⎞
sinh ⎜⎜ L ⎟⎟
⎝ DAB ⎠
This equation can be used at steady state to calculate cA at any z can be used for
reaction in gases, liquids, or even solids, where the solute A is dilute.
As an alternative derivation of Eq. (13.57), we can use Eq. (13.40) for constant ρ
and DAB.
∂c A
+ (ν . ∇c A ) − DAB ∇ 2 c A = RA . . . (13.59)
∂t
∂c A
We set the first term for steady state. Since we are assuming dilute solutions
∂t
and neglecting the bulk flow term, ν = 0, making the second term in Eq. (13.40)
zero. For a first-order reaction of A where A disappears, R A = − k ′ c A kg mol A
generated/s.m3.

Writing the diffusion term − D AB ∇ 2 c A for only the z direction, we obtain

d 2 cA
DAB = k ′ cA . . . (13.60)
dz
which is, of course, identical to Eq. (13.57).
SAQ 2
(a) Derive the continuity equation for a binary mixture.
(b) What do you mean by equimolar counter diffusion?
(c) How do you extend the unsteady state continuity equation to the steady state
condition?

13.7 UNSTEADY-STATE DIFFUSION AND REACTION IN A

SEMIINFINITE MEDIUM
Here we consider a case where dilute A is absorbed at the surface of a solid or stagnant
fluid phase and then unsteady-state diffusion and reaction occur in the phase. The fluid or
solid phase B is considered semiinfinite. At the surface where z = 0, the concentration of
cA is kept constant at cA0. The dilute solute A reacts by a first-order mechanism.
A+ B→C . . . (13.61)

and the rate of generation is − k ′ c A . The same diagram as in Figure 13.6 holds. Using
⎛ ∂c ⎞
Eq. (13.55) but substituting ⎜ A ⎟ (Δz ) (1) for the rate of accumulation,
⎝ ∂t ⎠
57
Mass Transfer ⎛ ∂c ⎞
N Az z (1) − k ′ c A (1) (Δz ) = N Az z = N Az z (1) + ⎜ A ⎟ (Δz ) (1) . . . (13.62)
⎝ ∂t ⎠
This becomes

∂c A ∂ 2cA
= DAB − k ′ cA . . . (13.63)
∂t ∂z 2
The initial and boundary conditions are
t=0 cA = 0 for z>0 . . . (13.64)
z=0 cA = cA0 for t>0
z=∞ cA – 0 for t>0
The solution is

cA 1 ⎛ k′ ⎞ ⎛ z ⎞
= exp ⎜⎜ − z ⎟⎟ . erfc ⎜⎜ − k′t ⎟ . . . (13.65)
c A0 2 DAB ⎟
⎝ ⎠ ⎝ 2 t DAB ⎠

1 ⎛ k′ ⎞ ⎛ z ⎞
+ exp ⎜⎜ z ⎟⎟ . erfc ⎜⎜ + k′t ⎟
2 DAB ⎟
⎝ ⎠ ⎝ 2 t DAB ⎠
The total amount Q of A absorbed up to time t is

DAB ⎡⎛ 1⎞ k′t ⎤
Q = c A0 ⎢⎜ k ′ t + ⎟ erf k′t + ⎥ . . . (13.66)
K′ ⎣⎢⎝ 2⎠ π e− k ′ t ⎦⎥

where Q is kg mol A absorbed/m3. Many actual cases are approximately by this case. The
equation is useful where absorption occurs at the surface of a stagnant fluid or a solid and
unsteady-state diffusion and reaction occurs in the solid or fluid. The results can be used
to measure the diffusivity of a gas in a solution, to determine reaction rate constant k′ of
dissolved gases, and to determine solubility of gas in liquids with which they react.

13.8 NUMERICAL METHODS FOR UNSTEADY-STATE

MOLECULAR DIFFUSION
Unsteady-state diffusion often occurs in inorganic, organic, and biologic solid materials.
If the boundary conditions are constant with time, if they are the same on all sides or
surfaces of the solid, and if the initial concentration profile is uniform throughout the
solid, the methods describes in Section 13.4 can be used. However, these conditions are
not always fulfilled. Hence, numerical methods must be used.
13.8.1 Unsteady-State Numerical Methods for Diffusion
Derivation for Unsteady State for a Slab
For unsteady-state diffusion in one direction

∂c A ∂ 2cA
= DAB . . . (13.67)
∂t ∂x 2
Since this equation is identical mathematically to the unsteady-state heat-
conduction Eq. (13.68),

∂T ∂ 2T
=α 2 . . . (13.68)
∂t ∂x

58
 identical mathematical methods can be used for solving both diffusion and Mass Transfer with
conduction numerically. Transient Diffusion and
Chemical Reaction
Figure 13.7 shows a slab with width Δx centered at point n represented by the
shaded area. Making a mole balance of A on this slab at the time t when the rate in
– rate out = rate of accumulation in Δt s,
DAB A D A ( A Δx)
( t cn −1 − t cn ) − AB ( t cn − t cn +1 ) = ( t + Δt cn − t cn ) . . . (13.69)
Δx Δx Δt
where A is cross-sectional area and t + Δt cn is concentration at point n one Δt later.

Rearranging,
1
t + Δt cn = [ t cn + 1 + ( M − 2) t cn + t cn −1 ] . . . (13.70)
M
where M is a constant.
(Δx) 2
M = . . . (13.71)
DAB Δt
As in heat conduction, M ≥ 2 .
In using Eq. (13.70), the concentration t + Δt cn at position n and the new time
t + Δt is calculated explicitly from the known three points at t. In this calculation
method, starting with the known concentrations at t = 0, the calculations proceed
directly from one time increment to the next until the final time is reached.
Simplified Schmidt Method for a Slab
If the value of M = 2, a simplification off Eq. (13.70) occurs, giving the Schmidt
method.
t cn − 1 + t cn + 1
t + Δt cn = . . . (13.72)
2
Δx / 2 Δx / 2

ca

c1
Δx Δx
c2

cn−1

cn
cn+1
in out
cf − 1
cf

in out

1 1.5 2 n −1 n n +1 f −1 f

Figure 13.7 : Unsteady-state Diffusion in a Slab

13.8.2 Boundary Conditions for Numerical Method for a Slab

Convection at a Boundary
For the case where convection occurs outside in the fluid and the concentration of
the fluid outside is suddenly changed to ca, we can make a mass balance on the
1
outside slab in Figure 13.7. Following the methods used for heat transfer we
2 59
Mass Transfer write rate of mass entering by convection – rate of mass leaving by diffusion = rate
of mass accumulation in Δt hours.
⎛ A Δx ⎞
⎜ ⎟
kc A ( t ca − t c1 ) − AB ( t c1 − t c2 ) = ⎝
D A 2 ⎠
( t + Δt c1.25 − t c1.25 ) . . . (13.73)
Δx Δt
where t c1.25 is the concentration at the midpoint of the 0.5 Δx outside slab. As an
approximation using t c1 for t c1.25 and rearranging Eq. (13.73),
1
t + Δt c1 = [ 2 N t ca + [M − (2 N + 2)]t c1 + 2t c2 ] . . . (13.74)
M
kc Δx
N= . . . (13.75)
DAB
where kc is the convective mass-transfer coefficient in m/s. Again, note that
M ≥ (2 N + 2) .
Insulated Boundary Condition
For the insulated boundary at f in Figure 13.7, setting kc = 0 ( N = 0) in
Eq. (13.74), we obtain
1
t + Δt cf = [( M − 2)t c f + 2t c f −1 ] . . . (13.76)
M
Alternative Convective Equation at the Boundary
Another form of Eq. (13.74) to use if N gets too large can be obtained by
neglecting the accumulation in the front half-slab of Eq. (13.73) to give
N 1
t + Δt c1 = t + Δt ca + t + Δt c2 . . . (13.77)
N +1 N +1
The value of M is not restricted by the N value in this equation. When a large
number of increments in Δx are used, the amount of mass neglected is small
compared to the total.
Procedure for Use of Initial Boundary Concentration
(ca + 0 c1 )
For the first time increment we should use an average value for 1ca of ,
2
where 0c1 is the initial concentration at point 1. For succeeding times, the full value
of ca should be used. The special procedure for the value of ca increases the
accuracy of the numerical method, especially after a few time intervals.
Boundary Conditions with Distribution Coefficients
Equations for boundary condition in Eqs. (13.74) and (13.77) were derived for the
distribution coefficients K given in Eq. (13.74) being 1.0. When K is not 1.0, as in
the boundary conditions for steady state, Kkc should be substituted for kc in
Eq. (13.75) to become as follows. (See also Sections 6.6 and 7.1.)
Kkc Δx
N= . . . (13.78)
DAB
ca
Also, in Eqs. (13.74) and (13.77), the term should be substituted for ca.
K
SAQ 3
(a) State the procedure of solving unsteady state diffusion equation numerically.
(b) What is insulated boundary condition?

60
 Mass Transfer with
Transient Diffusion and
Chemical Reaction

13.9 MASS DIFFUSION WITH HOMOGENEOUS

Chemical Reactions
Just as heat diffusion may be influenced by internal sources of energy, species
transfer by diffusion may be influenced by homogeneous chemical reactions. We
restrict our attention to stationary media. If we also assume steady,
one-dimensional transfer in the x direction and that DAB and C are constant,

d 2 CA
DAB + NA = 0 . . . (13.79)
dx 2
If there are no homogenous chemical reactions involving species A, the volumetric
species production rate, NA, is zero. When reactions do occur, they are often of the
form
Zero-order reaction
N A = k0 . . . (13.80)
First-order reaction
N A = k1 C A . . . (13.81)
That is, the reaction may occur at a constant rate (zero order) or at a rate that is
proportional to the local concentration (first order). The units of k0 and k1 are
kmol/s . m3 and s– 1, respectively. If NA is positive, the reaction results in the
generation of species A; if it is negative, it results in the consumption of A.
In many applications the species of interest is converted to another form through a
first-order chemical reaction, and Eq. (13.79) becomes

d 2 CA
DAB − k1 C A = 0 . . . (13.82)
dx 2
This linear, homogeneous differential equation has the general solution

C A ( x) = C1 e mx + C2 e − mx . . . (13.83)
1
⎛ k ⎞2
where m = ⎜ 1 ⎟ and the constants C1 and C2 depends on the prescribed
⎝ DAB ⎠
boundary conditions. The form of this equation is identical to that characterizing
heat conduction in an extended surface.
Gas A CA(x)
CA,O CA,O

x
Liquid B

x
NA= −K1CA
N″A x

L L
Impermeable Boundary

Figure 13.8 : Diffusion and Homogeneous Reaction of Gas A in Liquid B

Consider the situation illustrated in Figure 13.8. Gas A is soluble in liquid B, where
it is transferred by diffusion and experiences a first-order chemical reaction. The 61
Mass Transfer solution is dilute, and the concentration of A in the liquid at the interface is a
known constant CA, 0. If the bottom of the container is impermeable to A, at the
boundary conditions are
C A (0) = C A, 0 . . . (13.84)

dC A
and =0 . . . (13.85)
dx x=L

Using these boundary conditions with Eq. (13.83), it may be shown that
C A ( x) = C A, 0 (cosh m x − tanh m L sinh m x) . . . (13.86)

Quantities of special interest are the concentration of A at the bottom and the flux of A
across the gas-liquid interface. Applying Eq. (13.86) at x = L, we obtain
(cosh 2 m L − sinh 2 m L ) C A, 0
C A ( L ) = C A, 0 = . . . (13.87)
cos m L cosh m L

dC A
Moreover, N ′′A, x (0) = − DAB
dx x =0

= − DAB C A, 0 m (sinh m x − tanh m L cosh m x) x=0

. . . (13.88)

or N ′′A, x (0) = DAB C A, 0 m tanh m L . . . (13.89)

SAQ 4
(a) What is zero order chemical reaction?
(b) What is first order chemical reaction?
(c) What will be the mass diffusion in case of zero order and first order
chemical reactions?

Example 13.1 : Unsteady-State Diffusion in a Slab of Agar Gel

A solid slab of 5.15 wt % agar gel at 278 K is 10.16 mm thick and contains a
uniform concentration of urea of 0.1 kg mol/m3. Diffusion is only in the x direction
through two parallel flat surfaces 10.16 mm apart. The slab is suddenly immersed
in pure turbulent water so that the surface resistance can be assumed to be
negligible; i.e. the convective coefficient kc is very large. The diffusivity of urea in
the agar from Annexure II is 4.72 × 10– 10 m2/s.
(a) Calculate the concentration at the midpoint of the slab (5.08 mm from
the surface) and 2.54 mm from the surface after 10 h.
(b) If the thickness of the slab is halved, what would be the midpoint
concentration in 10 h?
Solution
For part (a), c0 = 0.10 kg mol/m3, c1 = 0 for pure water, and c = concentration at
distance x from center line and time t s. the equilibrium distance coefficient K in
Eq, (13.22) can be assumed to be 1.0, since the water in the aqueous solution in the
gel and outside should be very similar in properties. From Annexure 1,

62
 c1 0 Mass Transfer with
Transient Diffusion and
K −c 1.0 − c
Y = = Chemical Reaction
c1 0
K − c0 1.0 − 0.10

10.16
Also, x1 = = 5.08 × 10− 3 m (half-slab thickness), x = 0 (center),
(1000 × 2)
D t (10 × 3600)
X = AB = (4.72 × 10−10 ) = 0.658 . The relative position
2
x1 (5.08 × 10− 3 )
x 0 DAB
n= = −
= 0 and relative resistance m = = 0 , since kc is very
X1 5.08 × 10 3 Kkc x1
large (zero resistance).
From Annexure III for X = 0.658, m = 0, and n = 0,
0−c
Y = 0.275 =
0 − 0.10
Solving, c = 0.0275 kg mol/m3 for x = 0.
For the point 2.54 mm from the surface or 2.54 mm from center,
2.54 x 2.54 × 10− 3
x= = 2.54 × 10− 3 m, m = 0, n = = = 0.5 . Then from
1000 x1 5.08 × 10− 3
Figure 5.3-5, Y = 0.172. Solving, c = 0.0172 kg mol/m3.
0.658
For part (b) and half the thickness, X = = 2.632, n = 0 , and m = 0. Hence,
(0.5) 2
Y = 0.0020 and c = 2.0 × 10− 4 kg mol/m3.
Example 13.2 : Unsteady-State Diffusion in a Semiinfinite Slab
A very thick slab has a uniform concentration of solute A of
c0 = 1.0 × 10− 2 kg mol A/m3. Suddenly, the front face of the slab is exposed to a
flowing fluid having a concentration c1 = 0.10kg mol A/m3 and a convective
coefficient kc = 2 × 10− 7 m/s. The equilibrium distribution coefficient
c
K = Li = 2.0 . Assuming that the slab is a semiinfinite solid, calculate the
ci
concentration in the solid at the surface (x = 0) and x = 0.01 m from the surface
after t = 3 × 104 s. The diffusivity in the solid is DAB = 4 × 10− 9 m 2 /s.
Solution
To use Annexure IV,
Kkc 2.0 (2 × 10− 7 )
DAB t = −9
(4 × 10− 9 ) (3 × 104 ) = 1.095
DAB 4 × 10
For x = 0.01 m from the surface in the solid,
x 0.01
= = 0.457
2 DAB t 2 (4 × 10− 9 ) (3 × 104 )

From the chart, 1 – Y = 0.26. Then, substituting into the equation for (1 – Y) from
Table 7.1 and solving,
c − c0 c − 1 × 10− 2
1−Y = = = 0.26
c1 (10 × 10− 2 ) −2
− (1 × 10 )
K − c0 2
63
Mass Transfer
c = 2.04 × 10− 2 kg mol/m3 (for x = 0.01 m)
For x = 0 m (i.e. at the surface of the solid),
x
2 DAB t = 0

From the chart, 1 − Y = 0.62 Solving, c = 3.48 × 10− 2 . This value is the same as
ci, as shown in Figure 13.3(b). To calculate the concentration cLi in the liquid at the
interface,
C Li = Kci = 2.0 (3.48 × 10− 2 ) = 6.96 × 10− 2 kg mol/m3
A plot of these values will be similar to Figure 13.3(b).
Example 13..3 : Diffusion and Chemical Reaction at a Boundary
Pure gas A diffuses from point 1 at a partial pressure of 101.32 kPa to point 2 a
distance 2.00 mm away. At point 2 it undergoes a chemical reaction at the catalyst
surface and A → 2 B . Component B diffuses back at steady state. The total
pressure is P = 101.32 kPa. The temperature is 300 K and D AB = 0.15 × 10− 4 m 2 s.
(a) For instantaneous rate of reaction, calculate xA2 and NA.

(b) For a slow reaction where k1′ = 5.63 × 10− 3 m/s, calculate xA2 and NA.
Solution
For part (a), p A 2 = x A 2 = 0 since no A can exist next to the catalyst surface. Since
N B = − 2 N A , Eq. (13.48) will be used as follows :

δ = 2.00 × 10− 3 m, T = 300 K, . . .

P 101.32 × 103
= =
RT (8314 × 300)

= 4.062 × 10− 2 kg mol/m3 ,

p A1 101.32 × 103
x A1 = = = 1.00 .
P 101.32 × 103

cDAB 1 + x A1 (4.062 × 10− 2 ) (0.15 × 10− 4 ) 1 + 1.00

NA = ln = ln
δ 1 + x A2 2.00 × 10− 3 1+ 0

= 2.112 × 10 − 4 kg mol A/s.m 2

For part (b), from Eq. (13.50),
NA NA
x A2 = =
k1′ c (5.63 × 10 × 4.063 × 10− 2 )
− 3

Substituting into Eq. (13.51),

(4.062 × 10− 2 ) (0.15 × 10− 4 )
NA = ln
2.00 × 10− 3

1 + 1.00
=
1 + NA
(5.63 × 10− 3 × 0.062 × 10− 2 )
Solving by trial and error,

64
 N A = 1.004 × 10− 4 kg mol A/s.m 2
Mass Transfer with
Transient Diffusion and
Chemical Reaction
(1.004 × 10− 4 )
Then, x A2 = = 0.4390 .
(5.63 × 10− 3 × 4.062 × 10− 2 )
Exercise 13.1
(a) A very thick slab of clay has an initial moisture content of c0 = 14 wt%. Air
is passed over the top surface to dry the clay. Assume a relative resistance of
the gas at the surface of zero. The equilibrium moisture content at the
surface is constant at c1 = 3.0 wt%. The diffusion of the moisture in the clay
can be approximated by a diffusivity of D AB = 1.29 × 10− 8 m 2 /s. After
1.0 h of drying, calculate the concentration of water at points 0.005, 0.01,
and 0.02 m below the surface. Assume that the clay is a semiinfinite solid
and that the Y value can be represented using concentrations of wt% rather
than kg mol/m3. Plot the value versus x.
(b) A wet cylinder of agar gel at 278 K containing a uniform concentration of
urea of 0.1 kg mol/m3 has a diameter of 30.48 mm and is 38.1 mm long with
flat parallel ends. The diffusivity is 4.72 × 10− 10 m 2 /s. Calculate the
concentration at the midpoint of the cylinder after 100 h for the following
cases if the cylinder is suddenly immersed in turbulent pure water.
(i) For radial diffusion only.
(ii) Diffusion occurs radially and axially.
(c) A value of kG was experimentally determined to be 1.08 lb mol/h . ft2 . atm
for A diffusing through stagnant B. For the same flow and concentrations it
is desired to predict kG′ and the flux of A for equimolar counterdifffusion.
The partial pressures are p A1 = 0.20 atm, p A 2 = 0.05 atm, and P = 1.0 atm
abs total. Use English and SI units.
(d) Prove or show the following relationships starting with the flux equations.
(i) Convert kc′ to ky and kG.
(ii) Convert kL to kx and k x′ .
(iii) Convert kG to ky and kc.

Exercise 13.2
(a) Pure water at 26.1oC is flowing flowing at a velocity of 0.0305 m/s in a tube
having an inside diameter of 6.35 mm. The tube is 1.829 m long with the
last 1.22 m having the walls coated with benzoic acid. Assuming that the
velocity profile is fully developed, calculate the average concentration of
benzoic acid at the outlet. Use the physical property data of Example 7.3.
Dv p
[Hint : First calculate the Reynolds number . Then calculate
μ
⎛ D⎞ ⎛π⎞ W
N Re N Sc ⎜ ⎟ ⎜ ⎟ , which is the same as ]
⎝ L ⎠⎝4⎠ DAB ρ L
(b) It is desired to estimate the mass-transfer coefficient kG in kg mol/s.m2 Pa
for water vapor in air at 338.6 K and 101.32 kPa flowing in a large duct past
different geometry solids. The velocity in the duct is 3.66 m/s. The water 65
Mass Transfer vapor concentration in the air is small, so the physical properties of air can
be used. Water vapor is being transferred to the solids. Do this for the
following geometries.
(i) A single 25.4 mm-diameter sphere.
(ii) A packed bed of 25.4 mm spheres with ε = 0.35.
(c) Pure water at 26.1oC is flowing at a rate of 0.0701 ft3/h through a packed
bed of 0.251-in. benzoic acid spheres having a total surface area of 0.129 ft2.
The solubility of the benzoic acid in water is 0.00184 lb mol benzoic acid/ft3
solution. The outlet concentration cA2 is 1.80 × 10 − 4 lb mol/ft3. Calculate the
mass transfer coefficient kc.

Exercise 13.3
(a) Solute A is diffusing at unsteady state into a semiinfinite medium of pure B
and undergoes a first order reaction with B. Solute A is dilute. Calculate the
concentration cA at points z = 0, 4, and 10 mm from the surface for
t = 1 × 105 s. Physical property data are D AB = 1 × 10 − 9 m 2 /s ,
k ′ = 1 × 10− 4 s −1 , c A0 = 1.0 kg mol/m3. Also calculate the kg mol
absorbed/m2.
(b) A solid slab 0.01 m thick has an initial uniform concentration of solute A of
1.00 kg mol/m3. The diffusivity of A in the solid is DAB = 1.0 × 10−10 m 2 /s .
All surfaces of the slab are insulated except the top surface. The surface
concentration is suddenly dropped to zero concentration and held there.
Unsteady-state diffusion occurs in the one x direction with the rear surface
insulated. Using a numerical method, determine the concentrations after
12 × 104 s. Use Δx = 0.02 m and M = 2.0. The value of K is 1.0.

(c) Pure water at a velocity of 0.11 m/s is flowing at 26.1oC past a flat plate of
solid benzoic acid where L = 0.40 m. Do as follows :
(i) Assuming dilute solutions, calculate the mass-transfer
coefficient kc. Use physical property data from Example 7.3.
(ii) Using the film model, calculate the equivalent film thickness.
(iii) Using the penetration model, calculate the time of penetration.
(iv) Calculate the mean surface renewal factor using the modified
penetration model.

66
 Mass Transfer with
13.10 SUMMARY Transient Diffusion and
Chemical Reaction
Present unit describes the mass transfer phenomena under transient state and with
chemical reactions. Importance of the unsteady state mass transfer problems are
introduced at the beginning. General transient mass diffusion equation is derived and
same is extended for multi-dimensional system. Different methods of estimating mass
diffusion have been discussed. Special cases of transient diffusion with stationary
medium as well as binary mixtures are described. Numerical procedure to solve unsteady
state problems are discussed. Mass diffusion with chemical reactions is given at the end.
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.

13.11 KEY WORDS

Trasient : Time dependent.
Continuity : Mass conservation.
Equimolar : Equal number of moles of each species in a binary
mixture.
Doping : To control the conductivity of a silicon film of a
semiconductor device, very small amounts of a
specific atom, such as boron, are caused to diffuse
in to the region near the surface of the solid film.
This transient process is called doping.
Catalyst : It does not take part in a reaction but helps in
chemical reaction.

13.12 ANSWERS TO SAQs

Refer the preceding text for all the Answers to SAQs.

67
Mass Transfer

REFERENCES
R. B. Bird, W. E. Stewart, and E. N. Lightfoot (1960), Transport Phenomena, 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.
F. P. Incropera and D. P. Dewitt (2004), Fundamentals of Heat and Mass Transfer,
5th Edition, John Wiley and Sons.

68
 Mass Transfer with
Transient Diffusion and
Chemical Reaction

ANNUXURE I : RELATION BETWEEN MASS- AND

HEAT-TRANSFER PARAMETERS FOR
UNSTEADY-STATE DIFFUSION

Mass Transfer

Heat Transfer
cL cL
K = = 1.0 K = ≠ 1.0
c c

T1 − T c1 − c c1
Y,
T1 − T0 c1 − c0 K −c
c1
K − c0

T − T0 c1 − c c − c1
1 − Y,
T1 − T0 c1 − c0 c1
K − c0

αt D AB t D AB t
X, 2
x1 x12 x12

x x x
2 αt 2 DAB t 2 DAB t

k DAB DAB
m,
h x1 kc x1 K kc x1

h kc K kc
αt DAB t DAB t
k DAB DAB

x x x
n,
x1 x1 x1
69
Mass Transfer

ANNEXURE II : TYPICAL DIFFUSIVITIES OF SOLUTES IN

DILUTE BIOLOGICAL GELS IN AQUEOUS
SOLUTION

Wt % Gel Temperature Diffusivity

Solute Gel in Solution (m2/s) Reference
o
K C

Surcose Gelatin 0 278 5 0.285 × 10– 9 (F2)

3.8 278 5 0.209 × 10– 9 (F2)
10.35 278 5 0.107 × 10– 9 (F2)
5.1 293 20 0.252 × 10– 9 (F3)

Urea Gelatin 0 278 5 0.880 × 10– 9 (F2)

2.9 278 5 0.644 × 10– 9 (F2)
5.1 278 5 0.609 × 10– 9 (F3)
10.0 278 5 0.542 × 10– 9 (F2)
5.1 293 20 0.859 × 10– 9 (F3)

Methanol Gelatin 3.8 278 5 0.626 × 10– 9 (F3)

Urea Agar 1.05 278 5 0.727 × 10– 9 (F3)

3.16 278 5 0.591 × 10– 9 (F3)
5.15 278 5 0.472 × 10– 9 (F3)

Glycerin Agar 2.06 278 5 0.297 × 10– 9 (F3)

6.02 278 5 0.199 × 10– 9 (F3)

Dextrose Agar 0.79 278 5 0.327 × 10– 9 (F3)

Surcose Agar 0.79 278 5 0.247 × 10– 9 (F3)

Ethanol Agar 5.15 278 5 0.393 × 10– 9 (F3)

NaCl (0.05 M) Agarose 0 298 25 1.511 × 10– 9 (S7)

2 298 25 1.398 × 10– 9 (S7)

70
 Mass Transfer with
Transient Diffusion and
Chemical Reaction

ANNEXURE III : UNSTEADY-STATE HEAT CONDUCTION

IN A LARGE FLAT PLATE
1.0
m=∞
x x1
m=6 x1
plate

n = 1.0
0.8
m=2
0.6
0.4
0.2
0.0
m=2

0.10

m=1
n = 1.0

T1 − T m=1
0.8
Y, 0.6
T1 − To 0.4
0.2
m = 0.5 0.0

m = 0.5

m=0 m=0
0.010
n = 1.0

0.8
0.6
0.4
0.2 71
0.0

m=0
n=1 n = 0.8
Mass Transfer

ANNEXURE IV : UNSTEADY-STATE HEAT CONDUCTION

IN A SEMIINFINITE SOLID WITH
SURFACE CONVECTION

1.00

0.80 = n at
0.60 k
x
0.40
3
0.30
2 Semi infinite Solid
0.20
1

0.6
T − T0
1 − y, 0.10 0.4
T1 − T0 0.08
0.06
0.3
0.2
0.04
0.03
0.1
0.02 0.07

0.05

0.01
0 0.4 0.8 1.2 1.6
x
2 at

72
 Mass Transfer with
Transient Diffusion and
Chemical Reaction

MASS TRANSFER
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 in Unit 11. Species
conservation equation and mass diffusion equations are derived for Cartesian coordinate
system. Boundary conditions are specified to solve such problems. A discussion is given
on mass transfer coefficient and its variation with geometry. Determination of mass
transfer coefficient is also discussed.
Unit 12 is devoted to mass transfer in laminar and turbulent flow. Mass transfer in flow
over flat plate, inside a tube and other situations such as mass transfer in packed bed,
suspended particles, flow past a single sphere etc are also discussed in this unit. Prandtl
mixing length concept for turbulent mass transfer is discussed.
Mass transfer phenomena discussed in Units 11 and 12 were for steady state conditions
without any chemical reactions of species. However, unsteady state mass transfer is
important in many engineering problems. Further, species concentration and species
variation will alter due to chemical reactions. In order to address such cases, Unit 13 is
devoted to mass transfer in unsteady state as well as with chemical reactions. Derivation
of unsteady state mass diffusion is given. Numerical method to solve such problem is
also highlighted.

73