1

EXTERNAL DIFFUSION
EFFECTS ON
HETEROGENEOUS REACTIONS
A. Sarath Babu
2
SCOPE:

Fundamentals of Diffusion

External resistance to diffusion

The Shrinking core model
3 3
Mechanism of Heterogeneous Catalysis:
1. Bulk Diffusion of reacting molecules to the surface of the
catalyst
2. Pore Diffusion of reacting molecules into the interior pores
of the catalyst
3. Adsorption of reactants (chemisorption) on the surface of
the catalyst
4. Reaction on the surface of the catalyst between adsorbed
molecules
5. Desorption of products
6. Pore Diffusion of product molecules to the surface of the
catalyst
7. Bulk Diffusion of product molecules
4
Mechanism of Heterogeneous Catalysis:
5
In many industrial reactions, the overall rate of
reaction is limited by the rate of mass transfer
of reactants between the bulk fluid and the
catalytic surface.

Earlier, the diffusion steps were neglected by
assuming that these steps are fast when
compared to the other steps.

The external resistance to diffusion, and the
internal resistance to diffusion will be
discussed in this course.

6
The Algorithm:

1. Mole Balance
2. Rate law
3. Stoichiomery
4. Combine
5. Evaluate
7
The mole balance, need to be extend to include
the molar flux, W
AZ
and diffusional effects.

The molar flow rate of A in z direction down the
length of a tubular reactor, is the product of:
the flux, W
AZ
(mol/m
2
s), and
the cross-sectional area, A
C
, (m
2
)

AZ C AZ
W A F =
Fundamentals of Diffusion
In the case of plug flow

Need to extend to consider diffusion
superimposed on the molar average velocity.

c A AZ
A v C W / =
8 8
Molecules of a given species within a single phase will
always diffuse from regions of higher concentrations to
regions of lower concentrations.

This gradient results in a molar flux of the species A, W
A

(moles/area.time), in the direction of the concentration
gradient.

The W
A
, is relative to a fixed coordinate and is a vector
quantity with typical units of mol/m
2
s. In rectangular
coordinates:

Az Ay Ax A
kW jW iW W + + =
The mole balance to species A, which flows and reacts in an
element of volume V = x y z

Dividing by xyz and taking the limit as they go to
zero, the molar flux balance in rectangular coordinates

t
C
r
z
W
y
W
x
W
A
A
Az
Ay
Ax
c
c
= +
c
c

c
c

c
c

11
The corresponding balance in cylindrical coordinates with
no variation in the rotation about the z-axis is

Molar Flux
The molar flux of A, W
A
is the result of two contributions:
J
A
, the molecular diffusion flux relative to the bulk motion
of the fluid produced by a concentration gradient and B
A

the flux resulting from the bulk motion of the fluid:

The bulk flow term for species A is the total flux of all
molecules relative to a fixed coordinate times the mole
fraction of A:

t
C
r
z
W
rW
r r
A
A
AZ
Ar
c
c
= +
c
c

c
c
) (
1
A A A
B J W + =

=
i A A
W y B
12
The bulk flow term B
A
, can also be expressed in terms of
the concentration of A and the molar average velocity V:

Where the molar average velocity is:

V C B
A A
=
i i
V y V

=
For a binary system, the flux of A:

A A A
V C W =
The molar average velocity for a binary system is:

B B A A
V y V y V + =
The total molar flux:

V C J W
A A A
+ =
The total molar flux in terms of mole fractions:

) (
B A A A A
W W y J W + + =
13
Ficks First law:
Mass transfer:
Heat transfer:
Momentum transfer:
dz
dC
D J
A
AB Az
=
dz
dT
k q
t z
=
dz
du
t =
A AB A
y cD J V =
) (
B A A A AB A
W W y y cD W + + V =
V C C D W
A A AB A
+ V =
14
Binary Diffusion Evaluating the molar flux
Case I: Equimolar Counter Diffusion (EMCD):
for every mole of A that diffuses in a given
direction, one mole of B diffuses in the
opposite direction
EMCD in isomerization reaction

15
For constant total concentration:
A AB A B A A A A
y cD J W W y J W V = + + = ) (
A AB A A
C D J W V = =
Case II: Dilute Concentrations:
When the mole fraction of the diffusing
solute is small:
A AB A B A A A A
y cD J W W y J W V = ~ + + = ) (
second term neglected
This approximation is always used for molecules
diffusing within aqueous systems.
16
In Knudsen diffusion the reacting molecules
collide more with pore walls than with each other,
and molecules of different species do not affect
each other. Hence for Knudsen diffusion:
A K A A
C D J W V = =
Case III: Diffusion through a stagnant gas:
Limited number of situations
W
B
is zero
Case IV: Forced Convection:
Diffusion in the direction of flow is small in
comparison with bulk flow
J
AZ
= 0
17
c
A
A
c
A z A Az AZ
A
F
C
A
v
U C V C B W = = = = ~
When diffusional effects are neglected: F
A
= vC
A
Case V: Diffusion and convective transport
Az c Az
W A F =
z A
A
AB Az
U C
dz
dC
D W + =
In terms of concentration the flux is:

c z A
A
AB c Az Az
A U C
dz
dC
D A W F
(

+ = =
The molar flow rate is:

18
Flow, Diffusion and reaction:
t
C
r
z
C
U
y
C
U
x
C
U
z
C
y
C
x
C
D
A
A
A
z
A
y
A
x
A A A
AB
c
c
= +
c
c

c
c

c
c

c
c
+
c
c
+
c
c
2
2
2
2
2
2
For one-dimension at steady state:
0
2
2
= +
c
c

c
c
A
A
z
A
AB
r
z
C
U
z
C
D
19
Boundary Conditions
1. Specify a concentration at a boundary (z =0, C
A
= C
A0
).
For an instantaneous reaction at a boundary, the
concentration of the reactants at the boundary is taken
to be zero (C
AS
= 0)

2. Specify a flux at a boundary:
a) No mass transfer to a boundary, W
A
= 0
b) Set the molar flux to the surface equal to the rate of
reaction on the surface: W
A
= -r
A

c) Set the molar flux to the boundary equal to convective
transport across a boundary layer
W
A
(boundary) = k
c
(C
As
C
Ab
)

3. Planes of Symmetry, i.e., the concentration gradient is
zero in that plane of symmetry.
20
Modeling Diffusion without reaction
Chemically reacting systems in which diffusional effects are important
Step 1: Perform a differential balance for species A
Step 2: Substitute for F
AZ
in terms of W
AZ
Step 3: Replace W
AZ
by the concentration gradient
Step 4: State the boundary conditions
Step 5: Solve for the concentration profile
Step 6: Solve for the molar flux
21
Example: Diffusion Through a Film to a Catalyst Particle

Species A which is present in dilute concentrations is
diffusing at steady state from the bulk fluid through a
Stagnant film of B of thickness to the external surface of
the catalyst. The concentration of A at the external
boundary is C
Ab
and at the external catalyst surface is C
As

with C
Ab
> C
As
.

Because the thickness of the "hypothetical stagnant film"
next to the surface is small with respect to the diameter of
the particle (i.e., << d,), curvature is neglected and the
diffusion is represented in rectilinear coordinates.

Determine the concentration profile and the flux of A to
the surface using (a) shell balances and (b) the general
balance equations.

22
Given : D
AB
= 0.01 cm
2
/s; C
T0
= 0.1 kmol/m
3
y
Ab
= 0.9; y
As
= .2
Shell Balances: Perform a mole balance on species A over
a differential element of width z and
cross-sectional area A

Step 1: The general mole balance equation is:
rate in rate out + rate of gen. = rate of acc.

0 0 = +
A + z z AZ z AZ
F F
23
Dividing by Z gives:
Step 2: Substitute for F
AZ
in terms of W
AZ
and A
C
.
F
AZ
= W
AZ
A
c

Dividing by A
C
, we get:

Taking the limit as Z 0,
Step 3: Relate W
AZ
, to the concentration gradient. For a
dilute concentration of the diffusing solute, and for
constant total concentration:

Differentiating for constant diffusivity yields:

dz
dC
D W
A
AB Az
=
2
2
dz
C d
D
dz
dW
A
AB
Az
=
0 =
A

A +
Z
F F
z AZ z z AZ
0 =
dZ
dF
AZ
0 =
dZ
dW
AZ
24
Therefore, the differential equation describing diffusion
through a liquid film reduces to:

Step 4: The boundary conditions are:
when z = 0, C
A
= C
Ab
when z = , C
A
= C
A
Step 5: Solve For the concentration profile. The first
integration yields:

And the second yields: C
A
= k
1
z+ k
2

Using boundary conditions, evaluate k
1
and k
2
0
2
2
=
dZ
C d
A
1
k
dZ
dC
A
=
o
z
C C
C C
Ab As
Ab A
=

o
z
C C C C
Ab As Ab A
) ( + =
25
Concentration profile

Step 6: The next step is to determine the molar flux of A
diffusing through the stagnant film. For dilute solute
concentrations and constant total concentration:

dz
dC
D W
A
AB Az
=
(

+ =
o
z
C C C
dz
d
D W
Ab As Ab Ab Az
) (
) (
Ab As
Ab
Az
C C
D
W =
o
s m kmol y y
C D
W
As Ab
T Ab
Az
. / 07 . 0 ) (
2 0
= =
o
26
General Balance Equations:

t
C
r
z
W
y
W
x
W
A
A
Az
Ay
Ax
c
c
= +
c
c

c
c

c
c

The equation reduces to:

c
c

c
c

c
c
+
c
c
+
c
c
2
2
2
2
2
2
Alternately:

The equation reduces to:

0
2
2
=
dz
C d
D
A
AB
0 , 0 , 0 , 0
2
2
2
2
=
c
c
=
c
c
=
c
c
=
c
c
y
C
y
C
x
C
x
C
A A A A
27
Temperature & Pressure dependence of D
AB

Note: Knudsen, liquid and solid diffusivities are
independent of total pressure
28
29
Modeling Diffusion with Chemical Reaction

1. Define the problem and state the assumptions.
2. Define the system on which the balances are to be
made.
3. Perform a differential mole balance on a particular
species.
4. Obtain a differential equation in W
A
by rearranging the
balance equation properly and taking the limit as the
volume of the element goes to zero
5. Substitute the appropriate expression involving the
concentration gradient for W
A
, to obtain a second-order
differential equation for the concentration of A

30
6 Express the reaction rate r
A
, in terms of concentration
and substitute into the differential equation.
7 State the appropriate boundary and initial conditions.
8 Put the differential equations and boundary conditions.
in dimensionless form.
9 Solve the resulting differential equation for the
concentration profile.
10 Differentiate this concentration profile to obtain an
expression for the molar flux of A.
11 Substitute numerical values for symbols.

31
External Resistance to Mass Transfer

Reaction takes place only on the external catalyst
surface and not in the fluid surrounding it.
The fluid velocity in the vicinity of the spherical pellet
will vary with position around the sphere.
The hydrodynamic boundary layer is defined as the
distance from a solid object to where the fluid velocity
is 99% of the bulk velocity U
0
.
Similarly. the mass transfer boundary layer thickness,
is defined as the distance from a solid object to where
the concentration of the diffusing species reaches
99% of the bulk concentration.

32
The change in concentration of A from C
Ab
to C
As
,
takes place in a very narrow fluid Layer next to the
surface of the sphere.

All the resistance to mass transfer is lumped in this
layer.

33
Mass Transfer Coefficient

model diffusive transport by treating the fluid layer next
to a solid boundary as a stagnant film of thickness .
all the resistance to mass transfer is lumped within this
hypothetical stagnant film.
the properties (i.e., concentration, temperature) at the
outer edge of the stagnant film is identical to those of
the bulk fluid.
34
For EMCD or dilute concentrations:
) ( ) (
AS AB c AS AB
AB
Az
C C k C C
D
W = =
o
) / 1 ( Resistance
force Driving
c
AS AB
Az
k
C C
Flux W

= = =
The boundary layer thickness may vary around the sphere
assumed to have a mean film thickness .

The ratio of the diffusivity D
AB
to the film thickness is
the mass transfer coefficient, k
c

35
Correlations for the Mass Transfer Coefficient

The mass transfer coefficient k
c
is analogous to the
heat transfer coefficient h.

The heat flux q from the bulk fluid at a temperature T
o

to a solid surface at T
s
is:

The heat transfer correlation for flow around a sphere
(over a wide range of Re) is:


If a sphere is immersed in a stagnant fluid (Re = 0), then
Nu = 2.

At higher Re in which the boundary layer remains
laminar, the Nusselt number becomes:

) (
0 s r
T T h q =
3 / 1 2 / 1
Pr Re 6 . 0 2+ = Nu
t
p
k
hd
Nu =

p
d U
= Re
t t
p
t
p
k
C
k
C
o
v

=
|
|
.
|

\
|
= = Pr
3 / 1 2 / 1
Pr Re 6 . 0 ~ Nu
36
The heat and mass transfer correlations are analogous.

Sh Nu
Sc Pr

) (
AS AB c Az
C C k W =
The one-dimensional differential forms of the mass
flux for EMCD and the heat flux are:

The correlation for mass transfer for flow around a
spherical pellet is analogous to heat transfer:

Frossling Correlation

dz
dC
D W
A
AB Az
=
dz
dT
k q
t z
=
) (
0 s r
T T h q =
3 / 1 2 / 1
Re 6 . 0 2 Sc Sh + =
AB
p c
D
d k
Sh =
AB
D
Sc
v
=
37
Example: The isomerizatian A B, is taking place on the surface of a
solid sphere. The surface reaction follows a Langmuir-Hinshelwood
single-site mechanism for which the rate law is:











Diffusion to, and reaction on external surface of pellet

The temperature is sufficiently high such that the case of
very weak adsorption (i.e., low surface coverage) of A and B is only
considered:

Bs B As A
As r
As
C K C K
C k
r
+ +
=
1
' '
1 << +
Bs B As A
C K C K
As r As
C k r =
' '
38
Set the molar flux to the surface equal to the rate of reaction on the surface:
W
A
= -r
A


Set the molar flux to the boundary equal to convective transport across a
boundary layer: W
A
(boundary) = k
c
(C
Ab
C
As
) = k
r
C
As
Solving for C
AS
:

The flux is often written in terms of an effective transport coeff. k
eff
:

Case -1: Rapid Reaction:
Consider how the overall rate of reaction may be increased
when the rate of mass transfer to the surface limits the
overall rate of reaction.
c r
A c
As
k k
C k
C
+
=
c r
r c
eff
k k
k k
k
+
=
c r
A r c
As A
k k
C k k
r W
+
= =
' '
A eff As A
C k r W = =
' '
A c
r c
A c
A
C k
k k
C k
r ~
+
=
/ 1
' '
c r
k k >> 1 / <<
r c
k k
39
To increase the rate of reaction per unit surface area of solid sphere,
increase C
A
and / or k
c
. In this gas-phase catalytic reaction and for
most liquids, the Schmidt number is sufficiently larger than 2.

Neglecting 2:

Term (1) is a function of the physical properties D
AB
and v, which
depend on temperature and pressure only.

The diffusivity always increases with temp. for liquids.

Term (2) is a function of flow conditions and particle size.

To increase k, either decrease the particle size or increase
the velocity of the fluid flowing past the particle.

If the velocity is doubled, the mass transfer coefficient
and the rate of reaction is increased by a factor of:

) 2 )( 1 ( 6 . 0 6 . 0
2 / 1
2 / 1
6 / 1
3 / 2
Term Term
d
U D
k
p
AB
c
= =
v
41 . 1 2 ) / (
5 . 0 5 . 0
1 2
= = U U
40
Effect of velocity on reaction rate
(Mass transfer limited reactions / Rapid reaction)

Case II: Slow Reaction: The specific reaction rate constant is small
with respect to the mass transfer coefficient:

Mass transfer effects are not important when
the reaction rate is limiting. The specific
reaction rate is independent of the velocity of
fluid and independent of particle size.

However. For porous catalyst pellets, k
r
may
depend on particle size for certain situations.

A r
c r
A r
As
C k
k k
C k
r ~
+
=
/ 1
' '
c r
k k <<
41
Regions of mass transfer-limited
and reaction-limited reactions

Figure shows the variation in reaction rate with Term 2, the ratio of
velocity to particle size.
At low velocities the mass transfer boundary layer thickness is
large and diffusion limits the reaction.

As the velocity past the sphere is increased, the boundary layer
thickness decreases, and the mass transfer across the boundary
layer no longer limits the rate of reaction.

For a given velocity, reaction-limiting conditions can be achieved by
using very small particles.

42
Mass Transfer-Limited Reactions in Packed Beds

A number of industrial reactions are potentially mass
transfer-limited as they are carried out at high temp. to
eliminate the occurrence of undesirable side reactions.

In such cases, the surface reaction is so rapid that the
rate of transfer of reactant from the bulk gas or liquid
phase to the surface limits the overall rate of reaction.

Mass transfer-limited reactions respond quite
differently to changes in temperature and flow
conditions than do the rate-limited reactions.

The basic equations describing the variation of
conversion with the various reactor design parameters:
catalyst weight, flow conditions will be developed.

43
Consider the reaction being carried out in a packed bed reactor:

A steady state mole balance on reactant A for the elemental volume:

where r
A
= rate of gen. of A per unit surface area, mol/s. m
2
a
c
= external surface area of catalyst per volume of catalytic bed,
= 6( 1 - |)/d
p
, for packed beds, m
2
/m
3

| = porosity of the bed (i.e., void fraction)
d
p
= particle diameter, m
A
C
= cross-sectional area of tube containing the catalyst, m
2
0 ) (
' '
= A +
A +
Z A a r F F
c c A z z AZ z AZ
44
Dividing by A
C
Z and taking the limit as Z 0,

The molar flow rate of A in the axial direction is:

In the case of packed beds, material transported by diffusion or
dispersion in the axial direction is negligible compared with that
transported by convection/bulk flow. In other words axial diffusion
is neglected.

where U is the superficial molar average velocity through the bed, m/s

0
1
' '
= +
c A
Az
c
a r
dz
dF
A
c Az Az Az c Az
A B J W A F ) ( + = =
c A c Az Az c Az
A UC A B W A F = = =
The differential equation describing flow and reaction in packed bed
for constant U:

0
) (
' '
= +
c A
A
a r
dz
U C d
0
' '
= +
c A
A
a r
dz
dC
U
45
Diffusion across stagnant film surrounding catalyst pellet

For reactions at steady state, the molar flux of A to
the particle surface, W
Ar
is equal to the rate of
disappearance of A on the surface, r
A

For reactions that are completely mass
transfer limited it is not necessary to
know the rate laws.

In most mass transfer-limited reactions, the surface
concentration is negligible with respect to the bulk concentration
(C
A
>> C
As
)

0 ) ( =
As A c c
A
C C a k
dz
dC
U
A c c
A
C a k
dz
dC
U =
) (
' '
As A c Ar A
C C k W r = =
46
Integrating with the limit, at z = 0, C
A
= C
Ao
:

The corresponding variation of reaction
rate along the length of the reactor is:

Axial concentration and conversion profiles for a
mass transfer limited reaction in a packed bed.

The reactor length L necessary to achieve a conversion:
X = (C
A0
C
AL
)/C
A0
( ) z
C
C
U
a k
A
A c c

= exp
0
( ) z C k r
U
a k
A c A
c c

= exp
0
' '
L
x
U
a k
c c
=
1
1
ln
47
The Shrinking Core Model

Used to describe situations in which solid particles are
being consumed either by dissolution or reaction and as
a result, the amount of the material being consumed is
"shrinking."

This model applies to areas:
pharmacokinetics (dissolution of pills in the
stomach)
the formation of an ash layer around a burning
coal particle
catalyst regeneration.

To design the time release of drugs into the body's
system: the rate of dissolution of capsules and solid
pills injected into the stomach should be known

48
Catalyst Regeneration

One of the most common examples is the removal of carbon from
catalyst particles that have been deactivated by fouling

The catalyst regeneration process to reactivate the catalyst by
burning off the carbon is shown in Figure: (the removal of carbon
from a single porous catalyst pellet as a function of time)

Carbon is first removed from the outer edge of the pellet and
then in the final stages of the regeneration from the center core
of the pellet.

As the carbon continues to be removed from the
porous catalyst pellet, O
2
must diffuse farther
into the material as the reaction proceeds to
reach the unreacted solid phase.

The regeneration time can be reduced by
increasing the gas-phase O
2
conc. & temp.

49
A core of un-reacted carbon is contained between r = 0 and
r = R.

Carbon has been removed from the porous matrix between
r = R and r = R
0
. Oxygen diffuses from the outer radius
R
0
to the radius R, where it reacts with carbon to form
carbon dioxide, which then diffuses out of the porous
matrix.

The reaction at the solid surface is very rapid, so the rate
of oxygen diffusion to the surface controls the rate of
carbon removal from the core.
Partially regenerated catalyst pellet
50
Although the core of carbon is shrinking with time (unsteady-state
process), the concentration profiles at any instant in time is assumed
to be at steady-state over the distance (R
0
- R).

This assumption is referred to as the QSSA.

Oxygen must diffuse through the porous pellet until it reaches the
Unreacted carbon core.
To study how the radius of unreacted carbon changes with time, first
find the rate of diffusion of oxygen to the carbon surface.

51
Perform a mole balance on the elemental carbon and equate the rate
of consumption of carbon to the rate of diffusion of oxygen to the
gas-carbon interface.

Applying a differential oxygen mole balance over the increment r
located somewhere between R
0
and R.

Note that O
2
does not react in this region and reacts only when it
reaches the solid carbon interface located at r = R.

Let species A represent 0
2
.

Step 1: The mole balance on O
2
between r and r + r is

Dividing by 4 r and taking the limit gives:

0
) (
2 2
2
0
| |
lim
= =
A

A +
A
dr
r W d
r
Ar Ar Ar r r r
r
r W r W
0 0
2 2
| 4 | 4
= +
A +
r W r W
Ar Ar r r r
t t
52`
Step 2: For every mole of 0
2
that diffuses into the spherical pellet, 1
mole of CO
2
, diffuses out (W
C02
= - W
02
), that is, EMCD.

The constitutive equation for constant total concentration becomes:


where D
e
is an effective diffusivity in the porous catalyst.

Step 3: Combining the two equations yields:
Dividing by (-D
e
) gives:

Step 4: The boundary conditions are:
At the outer surface of the particle, r = R
0
: C
A
= C
AO
At the fresh carbon-gas interface, r = R(t): C
A
= 0 (rapid rea.)

Step 5: Integrating twice yields:

dr
dC
D W
A
e Ar
=
0
2
=
|
.
|

\
|
r
dr
dC
D
dr
d
A
e
0
2
=
|
.
|

\
|
r
dr
dC
dr
d
A
1
2
k
dr
dC
r
A
=
2
1
k
r
k
C
A
+

=
53
Using the boundary conditions to eliminate K
1
and K
2
, the concentration
profile is given by:

Oxygen concentration profile shown from the external radius of the
pellet (R
0
) to the pellet center. The gas-carbon interface is at R

Step 6: The molar flux of 0
2
, to the gas-carbon interface is:

0
/ 1 / 1
/ 1 / 1
0
R R
r R
A
A
C
C

=
2
0
0
) / 1 / 1 ( r R R
C D
dr
dC
D W
A e A
e Ar

= =
54
Step 7: We now carry out an overall balance on elemental carbon.
Elemental carbon does not enter or leave the particle.

Where:
c
is the molar density of the carbon

c
is the volume fraction of carbon in the porous catalyst.

Simplifying gives:

Step 8: The rate of disappearance of carbon is equal to the flux of
O
2
to the gas-carbon interface:

The minus sign arises with respect to W
Ar
because 0
2
is diffusing in
an inward direction [i.e., opposite to the increasing (r) direction]:

c c
c
r
dt
dR
|
' '
=
) / (
|
0
2
0 ' '
R R R
C D
W
r
A e
Ar
R r c

= =
=
dt
R d
r r
c c
c
|
.
|

\
|
=
+
| t
t
3
2 ' '
3
4
4
0 0
55
Step 9: Integrating with limits R = R
0
at t = 0, the time necessary for
the solid carbon interface to recede inward to a radius R is:

Oxygen concentration profile at various times. At t
1
the gas-carbon
interface is located at R(t
1
); at t
2
it is located at R(t
2
)

The time necessary to consume all the carbon
in the catalyst pellet is:

) / (
1
0
2
0
R R R
C D
dt
dR
c c
A e

=
|
(
(

|
|
.
|

\
|
+
|
|
.
|

\
|
=
3
0
2
0
0
2
0
2 3 1
6
R
R
R
R
C D
R
t
A e
c c
|
0
2
0
6
A e
c c
c
C D
R
t
|
=
56
Pharmacokinetics-Dissollution of Mono-dispersed Solid Particles
Consider the case where the total particle is being
completely consumed. Species A must diffuse to the
surface to react with solid at the liquid-solid interface.

Reactions of this type are typically zero order in B and
first order in A.

The rate of mass transfer to the surface is equal to
the rate of surface reaction.

For the case of small particles, the Frossling equation is approximated
by Sh = 2. (D is the diameter of the dissolving particle).

As r As As A c Ar
C k r C C k W = = =
' '
) (
A
r c
c r
As Ar
C
k k
k k
r W
+
= =
' '
D
D
k
e
c
2
=
*
' '
/ 1 2 / 1 / 1 D D
C k
D D k
C k
k k
C k
r
A r
e r
A r
c r
A r
As
+
=
+
=
+
=
57
where D* = 2D
e
/k
r
is the diameter at which the resistances to mass
transfer and reaction rate are equal.

D > D* mass transfer controls
D < D* reaction rate controls

A mole balance on the solid particle yields:
In - Out + Generation =Accumulation

Where, is the molar density of species B. For every 1 mol of A
dissolved 1 mol of B dissolves: Then r
As
= -r
Bs
,

After differentiation and rearrangement:

|
.
|

\
|
+
= =
*
' '
/ 1
1
2 ) ( 2
D D
C k r
dt
dD
A r As

|
.
|

\
|
+
=
*
/ 1 D D dt
dD
o

o
A r
C k 2
=
dt
D d
D r
Bs
) 6 / (
0 0
3
2 ' '
t
t = +
58
At time t = 0, the initial diameter is D = D
i

Integrating for the case of excess concentration of reactant A, the
relationship between diameter and time:

The time to complete dissolution of the solid particle is:

t D D
D
D D
i i
o = + ) (
2
1
2 2
*
|
|
.
|

\
|
+ =
*
2
2
1
D
D
D t
i
i
c
o
59
ANY CLARIFICATIONS ?