Chapter 2 – Fluid Particle Reactions

* Introduction

This chapter treats the class of heterogeneous reactions in which a gas

or liquid contacts a solid, reacts with it, and transforms it into product.
Such reactions may be represented by

A (fluid) + b B (so1id)  fluid or solid or fluid and solid products

As shown in Fig. solid particles remain unchanged in size during

reaction when they contain large amounts of impurities, which remain
as a non-flaking ash, or if they form a firm product material by the
reactions. Particles shrink in size during reaction when a flaking ash or
product material is formed or when pure B is used in the reaction.

Fluid – solid reactions are numerous and of great industrial importance.

Those in which the solid does not appreciably change in size during
reaction are as follows.

1. The roasting (or oxidation) of sulphide ores to yield the metal oxides.
For example, in the preparation of zinc oxide the sulphide ore is mined,
crushed, separated from the gangue by flotation, and then roasted in a
reactor to form hard white zinc oxide particles according to the reaction

2ZnS (s) + 3O2 (g)  2ZnO (S) + 2SO2 (g)

Similarly, iron pyrites react as

4FeS2 (s) + 11O2 (g)  2Fe2O3 (S) + 8SO2 (g)

2. The preparation of metals from their oxides by reaction in reducing

atmospheres. For example, iron is prepared from crushed and sized
magnetite ore in continuous counter current, three stage fluidized bed
reactors according to the reaction

Fe3O4 (S) + 4H2 (g)  3Fe (S) + 4H2O (g)

3. The nitrogenation of calcium carbide to produce cyanamide

CaC2 (S) + N2 (g)  CaCH2 (g) + C (amorphous)

4. The protective surface treatment of solids such as the plating of

metals.

The most common examples of fluid solid reactions in which the size
of solid changes are the reactions of carbonaceous materials such as
coal briquettes, wood, etc. with low ash content to produce heat or
heating fuels.

For example, with an insufficient amount of air, producer gas is formed

by the reactions
C (s) + O2 (g)  CO2 (g)

2C (s) + O2 (g)  2CO (g)

C (s) + CO2 (g)  2CO (g)

With steam, water gas is obtained by the reactions

C (s) + H2O (g)  CO (g) + H2 (g)

C (s) + 2H2O (g)  CO2 (g) + 2H2 (g)

Other examples of reactions in which solids change in size are as

follows.

1. The manufacture of carbon disulphide from the elements

C (s) + 2S (g)  CS2 (g)

2. The manufacture of sodium cyanide from sodium amide

NaNH2 (l) + C (s)  NaCN (l) + H2 (g)

3. The manufacture of sodium thiosulfate from sulphur and sodium

sulphite
Na2SO3 (solution) + S (s)  Na2S2O3 (solution)

Still other examples are the dissolution reactions, the attack of metal
chips by acids, and the rusting of iron.

* Discuss the selection of model for fluid particle reactions

For the noncatalytic reaction of particles with surrounding fluid, we

consider two simple idealized models, the progressive conversion
model and the shrinking unreacted core model.

Progressive Conversion Model (PCM)

Here we visualize that reactant gas enters and reacts throughout the
particle at all times, most likely at different rates at different locations
within the particle. Thus, solid reactant is converted continuously and
progressively throughout the particle as shown in Fig.
Shrinking Core Model (SCM)

Here we visualize that reaction occurs first at the outer skin of the
particle. The zone of reaction then moves into the solid, leaving behind
completely converted material and inert solid. We refer to these as
"ash." Thus, at any time there exists an unreacted core of material,
which shrinks in size during reaction, as shown in Fig.
* Discuss the various steps involved in shrinking core model for
spherical particles of unchanging size

This model was first developed by Yagi and Kunii (1955, 1961), who
visualized five steps occurring in succession during reaction (see Fig.
given below).

Step 1. Diffusion of gaseous reactant A through the film surrounding

the particle to the surface of the solid.

Step 2. Penetration and diffusion of A through the blanket of ash to the

surface of the unreacted core.

Step 3. Reaction of gaseous A with solid at this reaction surface.

Step 4. Diffusion of gaseous products through the ash back to the

exterior surface of the solid.

Step 5. Diffusion of gaseous products through the gas film back into
the main body of fluid.
* Establish relation of time with radius and conversion for a
spherical reacting particle of unchanging size when diffusion
through the gas film is the controlling resistance

Whenever the resistance of the gas film controls, the concentration

profile for gaseous reactant A is as shown in Fig.

From this figure, we see that no gaseous reactant is present at the

particle surface; hence, the concentration driving force, CAg - CAs
becomes CAg and is constant at all times during reaction of the particle.
Now since it is convenient to derive the kinetic equations based on
available surface, we focus attention on the unchanging exterior surface
of a particle S. Noting from the stoichiometry of reaction that dNB = b
dNA, we write

1 dNB 1 dNB b dNA

− =− = − = b k g (CAg − CAs )
S dt 4πR2 dt 4πR2 dt

1 dNB
∴− = b k g CAg = Constant … (1)
4πR2 dt
where kg is the mass transfer coefficient between fluid and particle.
Assume B be the molar density of B in the solid and V be the volume
of a particle, the amount of B present in a particle is

moles B
N B = ρB V = ( 3
) (m3 solid) … (2)
m solid

The decrease in volume or radius of unreacted core accompanying the

disappearance of dNB moles of solid reactant is then given by

4
− dNB = −b dNA = − ρB dV = − ρB d ( π rc3 ) = − 4 πρB rc2 drc
3

dNB drc
= 4 πρB rc2 … (3)
dt dt

From equations (1) and (3)

1 2
drc
− (4 πρ r
B c ) = b K g CAg
4πR2 dt

ρB 2
− (r dr ) = b K g CAg dt
R2 c c

On integrating above equation between the limits t = 0, rc = R and t = t,

rc = rc, we find how the unreacted core shrinks with time. Thus,

ρB rc 2 t
− 2 ∫ rc drc = b K g CAg ∫ dt
R R 0

r
ρB rc3 c
∴ − 2 { } = b K g CAg t
R 3 R
 ρB rc3 R3
∴− 2 { − } = b K g CAg t
R 3 3

ρB R3 rc3
∴ 2 { − } = b K g CAg t
R 3 3

ρB
∴ 2
{R3 − rc3 } = b K g CAg t
3R

ρB R 3 rc3
∴ {1 − 3 } = b K g CAg t
3 R2 R

ρB R rc 3
∴ {1 − ( ) } = b K g CAg t
3 R

ρB R rc 3
∴t= {1 − ( ) } … (4)
3 b K g CAg R

Let the time for complete conversion of a particle be , then by taking

rc = 0 in equation (4), we find

ρB R
τ= … (5)
3 b K g CAg

The radius of unreacted core in terms of fractional time for complete

conversion is obtained by combining equations (4) and (5)

t rc 3
= 1 − ( ) … (6)
τ R

This can be written in terms of fractional conversion by noting that

4
Volume of unreacted core π rc3 rc 3
1 − XB = = 3 =( )
Total volume of particle 4 R
π R3
3
 rc 3
∴ X B = 1 − ( ) … (7)
R

From equations (6) and (7)

t rc 3
= 1 − ( ) = XB
τ R

The above equation is the relationship of time with radius and

conversion when diffusion through the gas film is the controlling
resistance.

* Establish relation of time with radius and conversion for a

spherical reacting particle of unchanging size when diffusion
through the ash layer is the controlling resistance

To develop an expression between time and radius requires a two-step

analysis. First, examine a typical partially reacted particle, writing the
flux relationships for this condition. Then apply this relationship for all
values of rc in other words, integrate rc between R and 0.
Consider a partially reacted particle as shown in Fig. Both reactant A
and the boundary of the unreacted core move inward toward the centre
of the particle. However, for G/S systems, the shrinkage of the
unreacted core is slower than the flow rate of A toward the unreacted
core by a factor of about 1000, which is roughly the ratio of densities
of solid to gas. Because of this, it is reasonable for us to assume, in
considering the concentration gradient of A in the ash layer at any time
that the unreacted core is stationary.

The rate of reaction of A at any instant is given by its rate of diffusion

to the reaction surface as

dNA
− = 4πr 2 Q A = 4πR2 Q As = 4πrc2 Q Ac = Constant … (1)
dt

The flux of A within the ash layer be expressed by Fick's law for
equimolar counter diffusion as
dCA
Q A = De … (2)
dr

where De is the effective diffusion coefficient of gaseous reactant in the

ash layer. From equations (1) and (2)

dNA dCA
− = 4πr 2 De = Constant
dt dr

dNA dr
∴− = 4 π De dCA
dt r 2

Integrating above equation across the ash layer i.e. at rc = R, CA = CAg

= CAs and at rc = rc, CAc = 0

dNA rc dr CAc =0
− ∫ = 4 π De ∫ dCA
dt R r 2 CAg =CAs
 dNA −1 rc
∴− { } = 4 π De (0 − CAg )
dt r R

dNA 1 1
∴− { − } = 4 π De CAg … (3)
dt rc R

This expression represents the conditions of a reacting particle at any

time.

In the second part of the analysis, we let the size of unreacted core
change with time. For a given size of unreacted core, dNA/dt is
constant; however, as the core shrinks the ash layer becomes thicker,
lowering the rate of diffusion of A. The equation (3) contains three
variables, t, NA, and rc one of which must be eliminated or written in
terms of the other variables before integration the equation (3). Let us
eliminate NA by writing it in terms of rc. This relationship is given by
equation
4
− dNB = −b dNA = − ρB dV = − ρB d ( π rc3 ) = − 4 π ρB rc2 drc
3

∴ −b dNA = − 4 π ρB rc2 drc

dNA 4 π ρB 2 drc
∴− =− rc … (4)
dt b dt

From equations (3) and (4)

4 π ρB 2 drc 1 1
− rc { − } = 4 π De CAg
b dt rc R

1 1 b De CAg
∴ rc2 { − } drc = − dt
rc R ρB
 rc2 b De CAg
∴ {rc − } drc = − dt
R ρB

b De CAg rc2
∴− dt = {rc − } drc
ρB R

On integrating above equation between the limits t = 0, rc = R and t = t,

rc = rc, we have

b De CAg t rc
rc2
− ∫ dt = ∫ {rc − } drc
ρB 0 R R

r
b De CAg rc2 rc3 c
∴− t={ − }
ρB 2 3R R

b De CAg rc2 rc3 R2 R3

∴− t= { − }− { − }
ρB 2 3R 2 3R

b De CAg rc2 rc3 R2 R2

∴− t= − − +
ρB 2 3R 2 3

b De CAg rc2 rc3 R2

∴− t= − −
ρB 2 3R 6

b De CAg R2 rc3 rc2

∴ t= + −
ρB 6 3R 2

b De CAg R2 rc3 rc2

∴ t= (1 + 2 3 − 3 2 )
ρB 6 R R

ρB R 2 rc 3 rc 2
∴t= {1 + 2 ( ) − 3 ( ) } … (5)
6 b De CAg R R
Let the time for complete conversion of a particle be , then by taking
by taking rc = 0 in equation (5), we find

ρB R 2
τ= … (6)
6 b De CAg

The radius of unreacted core in terms of fractional time for complete

conversion is obtained by combining equations (5) and (6)

t rc 3 rc 2
= 1 + 2 ( ) − 3 ( ) … (7)
τ R R

This can be written in terms of fractional conversion by noting that

4
Volume of unreacted core π rc3 rc 3
1 − XB = = 3 =( )
Total volume of particle 4 3 R
πR
3

rc 3
1 − XB = ( )
R

rc 3 rc 2 2
( ) = 1 − XB and ( ) = (1 − X B ) 3 … (8)
R R

From equations (7) and (8), we find

t rc 3 rc 2 2
= 1 + 2 ( ) − 3 ( ) = 1 + 2(1 − X B ) − 3(1 − X B ) 3
τ R R

The above equation is the relationship of time with radius and

conversion when diffusion through the ash layer is the controlling
resistance.

* Establish relation of time with radius and conversion for a

spherical reacting particle of unchanging size when chemical
reaction controls
Fig. illustrates concentration gradients within a particle when chemical
reaction controls.

Since the progress of the reaction is unaffected by the presence of any

ash layer, the rate is proportional to the available surface of unreacted
core. Thus, based on unit surface of unreacted core, rc the rate of
reaction is written as
1 dNA b dNA
− = k C
𝑠 Ag  − = b k 𝑠 CAg
4πr𝑐2 dt 4πr𝑐2 dt

1 dNB
∴− = b k 𝑠 CAg … (1)
4πr𝑐2 dt

where ks is the first order rate constant for the surface reaction.

We know that
moles B
N B = ρB V = ( 3
) (m3 solid) … (2)
m solid

The decrease in volume or radius of unreacted core accompanying the

disappearance of dNB moles of solid reactant is then given by
 4
− dNB = −b dNA = − ρB dV = − ρB d ( π rc3 ) = − 4 π ρB rc2 drc
3

dNB drc
= 4 π ρB rc2 … (3)
dt dt

From equations (1) and (3)

1 2
drc
− (4 π ρ r
B c ) = b k s CAg
4πrc2 dt

− ρB drc = b k s CAg dt

On integrating above equation between the limits t = 0, rc = R and t = t,

rc = rc, we find how the unreacted core shrinks with time. Thus,

rc t
− ρB ∫ drc = b k s CAg ∫ dt
R 0

r
∴ − ρB {rc } Rc = b k s CAg t

∴ − ρB {rc − R} = b k s CAg t

∴ ρB {R − rc } = b k s CAg t

rc
∴ ρB R {1 − } = b k s CAg t
R

ρB R rc
∴t= {1 − } … (4)
b k s CAg R

Let the time for complete conversion of a particle be , then by taking

rc = 0 in equation (4), we find
 ρB R
τ= … (5)
b k s CAg

The radius of unreacted core in terms of fractional time for complete

conversion is obtained by combining equations (4) and (5)

t rc
= 1 − … (6)
τ R

This can be written in terms of fractional conversion by noting that

4
Volume of unreacted core π rc3 rc 3
1 − XB = = 3 =( )
Total volume of particle 4 R
π R3
3

rc 1
= (1 − X B ) 3 … (7)
R

From equations (6) and (7)

t rc 1
= 1− = 1 − (1 − X B ) 3
τ R

The above equation is the relationship of time with radius and

conversion when resistance to chemical reaction is the controlling.

* Discuss the combination of resistance and derive equation for

overall rate of reaction at any particular level of conversion on
combining the individual resistances

The above conversion-time expressions assume that a single resistance

controls throughout reaction of the particle. However, the relative
importance of the gas film, ash layer, and reaction steps will vary as
particle conversion progresses. For example, for a constant size particle
the gas film resistance remains unchanged, the resistance to reaction
increases as the surface of unreacted core decreases, while the ash layer
resistance is non-existent at the start because no ash is present, but
becomes progressively more and more important as the ash layer builds
up. In general, then, it may not be reasonable to consider that just one-
step controls throughout reaction.

To account for the simultaneous action of these resistances is

straightforward since they act in series and are linear in concentration.
Thus on combining equations of gas diffusion control, ash diffusion
control and chemical reaction control with their individual driving
forces and eliminating intermediate concentrations we can show that
the time to reach any stage of conversion is the sum of the times needed
if each resistance acted alone, or

t total = t film + t ash + t reaction

alone alone alone

For combining of equations, the equation of driving force for film

diffusion control is given by

1 dNB
− = b k g (CAg − CAs )
S dt

1 b (CAg − CAs )
∴ = … (1)
kg 1 dNB
−
S dt

The equation of driving force for ash diffusion control is given by

dNA 1 1 1 dNB 1 1
− { − }=− { − } = 4 π De (CAs − CAc )
dt rc R b dt rc R
 dNB R − rc
∴− { } = 4 b π De (CAs − CAc )
dt R rc

1 dNB R − rc 4 b π De (CAs − CAc )

∴− { }=
S dt R rc S

1 dNB R − rc 4 b π De (CAs − CAc )

∴− { }=
S dt R rc 4 π R2

1 dNB R − rc b De (CAs − CAc )

∴− { }=
S dt rc R

R (R − rc ) b (CAs − CAc )
∴ = … (2)
De rc 1 dNB
−
S dt

The equation of driving force for chemical reaction control is given by

1 dNB b dNA
− = − = b k s CAc
4πrc2 dt 4πrc2 dt

dNB
∴− = 4 π rc2 b k s CAc
dt

1 dNB 4 π rc2 b k s CAc

∴− =
S dt 4 π R2

1 dNB rc2 b k s CAc

∴− =
S dt R2

R2 b CAc
∴ = … (3)
k s rc2 − 1 dNB
S dt
Adding equations (1), (2) and (3), we find

1 R (R − rc ) R2
+ +
kg De rc k s rc2
b (CAg − CAs ) b (CAs − CAc ) b CAc
= + +
1 dNB 1 dNB 1 dNB
− − −
S dt S dt S dt

1 R (R − rc ) R2
∴ + +
kg De rc k s rc2
b
= (C − CAs + CAs − CAc + CAc )
1 dNB Ag
−
S dt

1 R (R − rc ) R2 b CAg
∴ + + =
kg De rc k s rc2 − 1 dNB
S dt

Rearranging above equation, we find

1 dNB b CAg
− =
S dt 1 R (R − rc ) R2
+ +
kg De rc k s rc2

or

1 2
drc b CAg
− 4πρ r
B c =
4πR2 dt 1 R (R − rc ) R2
+ +
kg De rc k s rc2

rc2 drc b CAg

∴ − 2 ρB =
R dt 1 R (R − rc ) R2
+ +
kg De rc k s rc2
 CAg
drc ) b(
ρB
∴− = 2
dt rc 1 R (R − rc ) R2
( + + )
R2 k g De rc k s rc2

CAg
drc b( )
ρB
∴− =
dt rc2 rc (R − rc ) 1
R2 k g De R ks
+ +
film ash reaction

As may be seen, the relative importance of the three individual

resistances varies as conversion progresses, or as rc decreases. On
considering the whole progression from fresh to completely converted
constant size particle, we find on the average that the relative roles of
these three resistances is given by

̅̅̅̅̅̅
1 dN A CAg
− =
S dt 1 R 3
+ +
k g 2 De ks

For ash free particles, which shrink with reaction only two resistances
such as gas film and surface reaction, need to be considered. Because
these are both based on the changing exterior surface of particles, we
may combine them to give at any instant

1 dNA CAg
− =
S dt 1 1
+
kg ks

* Discuss the various steps involved in shrinking core model for

spherical particles of changing size

When no ash forms, as in the burning of pure carbon in air, the reacting
particle shrinks during reaction, finally disappearing. This process is
illustrated in Fig. given below.
For a reaction of this kind, we visualize the following three steps
occurring in succession.

Step 1. Diffusion of reactant A from the main body of gas through the
gas film to the surface of the solid.

Step 2. Reaction on the surface between reactant A and solid.

Step 3. Diffusion of reaction products from the surface of the solid

through the gas film back into the main body of gas.

Note that the ash layer is absent and does not contribute any resistance.
As with particles of constant size, let us see what rate expressions result
when one or the other of the resistances controls.

* Discuss relation of time with radius and conversion for a

shrinking spherical particle when resistance to chemical reaction
controls

When chemical reaction controls, the behaviour is identical to that of

particles of unchanging size; therefore, Fig. and Eq. of chemical
reaction control in case of reaction of spherical particles of unchanging
size will represent the conversion-time behaviour of single particles.
Hence, Fig. and Eq. of chemical reaction control are identical for both
shrinking and of constant size of particle.

* Establish relationship of size and time for shrinking particles in

the Stokes regime if diffusion through gas film control

Film resistance at the surface of a particle is dependent on numerous

factors, such as the relative velocity between particle and fluid, size of
particle, and fluid properties. These have been correlated for various
ways of contacting fluid with solid, such as packed beds, fluidized beds,
and solids in free fall.

As an example, for mass transfer of a component of mole fraction y in

a fluid to free-falling solids gives

1 1
k g dP y 1 1 μ 3 dP u ρ 2
= 2 + 0.6 (Sc ) 3 (R e ) 2 = 2 + 0.6 ( ) ( ) … (1)
De ρ De μ

During reaction a particle changes in size; hence kg also varies. In

general, kg rises for an increase in gas velocity and for smaller particles.
Above equation (1) shows that

1
kg ~ for small dP and u … (2)
dP

1
u2
kg ~ 1 for large dP and u … (3)
dP 2

Equation (2) represents particles in the Stokes law regime. Let us

develop conversion-time expressions for such particles.
At the time when a particle, originally of size Ro has shrunk to size R,
we may write
4
dNB = ρB dV = ρB d ( π R3 ) = 4 π ρB R2 dR
3

dNB dR
∴ = 4 π ρB R2
dt dt

1 dNB 4 π ρB R2 dR dR
∴− =− = = − ρ B = b k g CAg … (4)
S dt 4 π R2 dt dt

Since particle in the Stokes regime and for pure reactant gas, equation
(1) reduces to

k g dP 2 De De
= 2 ⟹ kg = ⟹ kg = … (5)
De dP R

From equations (4) and (5)

dR De
− ρB =b C
dt R Ag

b De CAg
∴ − R dR = dt
ρB

We have on integrating above equation

R b De CAg t
− ∫ R dR = ∫ dt
Ro ρ B 0

R2 − R2o b De CAg
∴− ( ) = t
2 ρB

b De CAg R2o − R2
∴t =
ρB 2
 b De CAg R2o R2
∴t = (1 − 2 )
ρB 2 Ro

ρB R2o R 2
∴t= {1 − ( ) } … (6)
2 b De CAg Ro

The time for complete disappearance of a particle is thus

ρB R2o
τ= … (7)
2 b De CAg

On combining equations (6) and (7), we obtain

t R 2
= 1 − ( ) … (8)
τ Ro

This can be written in terms of fractional conversion by noting that

4
Volume of unreacted core π R3 R 3
1 − XB = = 3 =( )
Total volume of particle 4 3 Ro
π Ro
3

R 2 2
( ) = (1 − X B ) 3 … (9)
Ro

From equations (8) and (9), we find

t R 2 2
= 1 − ( ) = 1 − (1 − X B ) 3
τ Ro

* Discuss about determination of the rate-controlling steps

The following observations are a guide to experimentation and to the

interpretation of experimental data.
Temperature

The chemical step is usually much more temperature-sensitive than the

physical steps; hence, experiments at different temperatures should
easily distinguish between ash or film diffusion on the one hand and
chemical reaction on the other hand as the controlling step.

Time

Fig. (a) and (b) reveals the progressive conversion of spherical solids
when chemical reaction, film diffusion, and ash diffusion in turn
control.

Fig. (a)

Results of kinetic runs compared with these predicted curves should

indicate the rate-controlling step. Unfortunately, the difference
between ash diffusion and chemical reaction as controlling steps is not
great and may be masked by the scatter in experimental data.
 Fig. (b)

Particle size

Equations of time for gas diffusion control, ash diffusion control and
chemical reaction control with equation for mass transfer of a
component of mole fraction y in a fluid to free-falling solids show that
the time needed to achieve the same fractional conversion for particles
of different but unchanging sizes is given by

t ∝ R 1.5−2 for film diffusion controlling (the exponent drops as

Reynolds number rises)

t ∝ R 2 for ash diffusion controlling

t ∝ R for chemical reaction controlling

Thus, kinetic runs with different sizes of particles can distinguish

between reactions in which the chemical and physical steps control.
Ash versus film resistance

When a hard solid ash forms during reaction, the resistance of gas phase
reactant through this ash is usually much greater than through the gas
film surrounding the particle. Hence, in the presence of a non-flaking
ash layer, film resistance can safely be ignored. In addition, ash
resistance is unaffected by changes in gas velocity.

Predictability of film resistance

The magnitude of film resistance can be estimated from dimensionless

correlations such as

1 1
k g dP y 1 1 μ 3 dP u ρ 2
= 2 + 0.6 (Sc ) 3 (R e ) 2 = 2 + 0.6 ( ) ( )
De ρ De μ

Thus, an observed rate approximately equal to the calculated rate

suggests that film resistance controls.

Overall versus individual resistance

If a plot of individual rate coefficients is made as a function of

temperature, as shown in Fig. given below, the overall coefficient given
by the following equation cannot be higher than any of the individual
coefficients.

̅̅̅̅̅̅
1 dN A CAg 1 dNA CAg
− = or − =
S dt 1 R 3 S dt 1 1
+ + +
k g 2 De ks kg ks

Because of the series relationship among the resistances to reaction, the

net or observed rate is never higher than for any of the individual steps
acting alone.
With these observations, we can usually discover with a small,
carefully planned experimental program, which is the controlling
mechanism.

* Discuss limitations of shrinking core model

The various limitations of shrinking core model are as follows.

(i) The assumptions of this model may not match reality precisely. For
example, reaction may occur along a diffuse front rather than along a
sharp interface between ash and fresh solid, thus giving behaviour
intermediate between the shrinking core and the continuous reaction
models.

(ii) For fast reaction, the rate of heat release may be high enough to
cause significant temperature gradients within the particles or between
particle and the bulk fluid. Despite these complications, it is concluded
from studies of numerous systems that the shrinking core model is the
best simple representation for the majority of gas-solid reacting
systems. There are, however, two broad classes of exceptions to this
conclusion.

The first comes with the slow reaction of a gas with a very porous solid.
Here reaction can occur throughout the solid, in which situation the
continuous reaction model may be expected to better-fit reality. An
example of this is the slow poisoning of a catalyst pellet.

The second exception occurs when solid is converted by the action of

heat, and without needing contact with gas. Baking bread, boiling
missionaries, and roasting puppies are mouth-watering examples of
such reactions. Here again the continuous reaction model is a better
representation of reality.

Example: A batch of solids of uniform size is treated by gas in a

uniform environment. Solid is converted to give a non-flaking product
according to the shrinking-core model. Conversion is about 7/8 for a
reaction time of 1 h; conversion is complete in two hours. What
mechanism is rate controlling?

Solution: From given data: t = 1 h, XB = 7/8 and  = 2 h

If diffusion through gas film controls, it sholud satisfy equation

t
= XB
τ

t 1 7
LHS = = = 0.5 and RHS = X B = = 0.875
τ 2 8

LHS  RHS

The diffusion through gas film is not a controlling mechanism.

If diffusion through ash layer controls, it sholud satisfy equation

 t 2
( ) ( )
= 1 + 2 1 − XB − 3 1 − XB 3
τ

t 1 2
LHS = = = 0.5 & RHS = 1 + 2(1 − X B ) − 3(1 − X B ) 3 = 0.5
τ 2

LHS = RHS

The diffusion through ash layer may be controlling mechanism.

If resistance to reaction controls then it sholud satisfy equation

t 1
= 1 − (1 − X B ) 3
τ

t 1 1
LHS = = = 0.5 and RHS = 1 − (1 − X B ) 3 = 0.5
τ 2

LHS = RHS

The resistance to reaction controls may be controlling mechanism.

However, in absence of other data, it is difficult to predict whether
diffusion through ash layer controls or resistance to the chemical
reaction is controlling mechanism.

Example: Calculate the time needed to burn to completion particles

of graphite (R, = 5-mm,  = 2.2 gm/cm3, ks = 20 cm/sec) in an 8%
oxygen stream. For the high gas velocity used, assume that film
diffusion does not offer any resistance to transfer and reaction.
Reaction temperature = 900°C.

Solution: As per given information, for the high gas velocity used,
assume that film diffusion does not offer any resistance to mass transfer
and reaction. The graphite is pure form of carbon and reaction between
carbon and oxygen produce very soft product on burning. Hence, there
is non-existence of ash layer. Ultimately, we need to find out time
required for complete conversion of graphite particle when resistance
to chemical reaction controls.

The reaction mechanism for burning of graphite particle in presence of

oxygen is written as
C (s) + O2 (g)  CO2 (g) … (1)

2C (s) + O2 (g)  2CO (g) … (2)

From given data: R = 5-mm = 0.5-cm, ks = 20 cm/sec and  = 2.2

gm/cm3  B = 2.2/12 = 0.1833 mol/ cm3, b = 1 and b = 2 for reactions
(1) and (2) respectively.

Since 8 % oxygen stream means that 1 mole of air contains 0.08 mole
of oxygen at 900 oC. The volume of 1 mole of air at 900 oC is

900 + 273
V = 22.4 × = 96.24 liters = 96240 cm3
273

The concentration of oxygen is

0.08 mol
CAg = = 8.312 × 10−7
96240 cm3

The time needed to burn to completion particles of graphite when

chemical reaction control for reaction (1) is calculated as

ρB R
τreaction =
alone b k s CAg

0.1833 × 0.5
∴ τreaction =
alone 1 × 20 × 8.312 × 10−7

∴ τreaction = 5513. 113 sec = 1.5314 h

alone
The time needed to burn to completion particles of graphite when
chemical reaction control for reaction (2) is calculated as

ρB R
τreaction =
alone b k s CAg

0.1833 × 0.5
∴ τreaction =
alone 2 × 20 × 8.312 × 10−7

∴ τreaction = 2856.55 sec = 0.7657 h

alone

Note: If temperature of reaction is not given then volume of 1 mole

of air and is concentration is calculated as

𝑉 = 22.4 𝑙𝑖𝑡𝑒𝑟𝑠 = 22400 𝑐𝑚3

The concentration of oxygen is

0.08 𝑚𝑜𝑙
𝐶𝐴𝑔 = = 3.5714 × 10−6
22400 𝑐𝑚3

Example: Spherical particles of zinc blende of size R = 1-mm are

roasted in an 8% oxygen stream at 900°C and 1 atm. The
stoichiometry of the reaction is
2ZnS (s) + 3O2 (g)  2ZnO (s) + 2SO2 (g)
Assuming that reaction proceeds by the shrinking-core model.
Calculate the time needed for complete conversion of a particle and
the relative resistance of ash layer diffusion during this operation.

Data: Molar density of solid B = 0.0425 mol/cm3, reaction rate

constant ks = 2 cm/sec, for gases in the ZnO layer De = 0.08 cm2/sec.
Note that film resistance can safely be neglected as long as a growing
ash layer is present. Repeat for particle size of R = 0.05-mm.
Solution: From given information, film resistance can safely be
neglected as long as a growing ash layer is present. Spherical particles
of zinc blende are roasted in an 8% oxygen stream at 900°C and 1 atm
produce non-flaking zinc oxide as a product that confirm the presence
of ash layer. Finally, the resistance to ash layer diffusion and chemical
reaction acts in series during the reaction.

From given data, particle size R = 1-mm = 0.1-cm, molar density of

solid B = 0.0425 mol/cm3, reaction rate constant ks = 2 cm/sec, for
gases in the ZnO layer De = 0.08 cm2/sec, from reaction stoichiometry
of reaction b = 2/3, T = 900 oC = 1173 K and P = 1 atm.

Since 8 % oxygen stream means that 1 mole of air contains 0.08 mole
of oxygen at 900 oC. The volume of 1 mole of air at 900 oC is

900 + 273
V = 22.4 × = 96.24 liters = 96240 cm3
273

The concentration of oxygen is

0.08 mol
CAg = = 8.312 × 10−7
96240 cm3

The concentration of oxygen is calculated by other method as

The partial pressure of oxygen = mole fraction of oxygen  pressure

𝑃𝐴𝑔 = 𝑦 × 𝑃

∴ 𝑃𝐴𝑔 = 0.08 × 1 = 0.08 𝑎𝑡𝑚

The concentration of oxygen is

𝑃𝐴𝑔 0.08 𝑚𝑜𝑙

𝐶𝐴𝑔 = = = 8.312 × 10−7
𝑅𝑇 82.06 × 1173 𝑐𝑚3
The time needed for complete conversion of a particle when diffusion
through ash layer controls alone is calculated as

ρB R2
τ ash =
alone 6 b De CAg

0.0425 × (0.1)2
∴τ ash =
2
alone 6× × 0.08 × 8.312 × 10−7
3

∴τ ash = 1597.45 sec = 0.4437 h

alone

The time needed for complete conversion of a particle when resistance

to reaction controls alone is calculated as

ρB R
τreaction =
alone b k s CAg

0.0425 × 0.1
∴ τreaction =
2
alone × 2 × 8.312 × 10−7
3

∴ τreaction = 3834.81 sec = 1.065 h

alone

The time needed for complete conversion of a particle when both

diffusion through ash layer and chemical reaction controls is

τtotal = τ ash + τreaction = 1597.45 + 3834.81 = 5432.26 sec

alone alone

τ ash
alone
Resistance to ash layer diffusion = × 100
τtotal

1597.45
∴ Resistance to ash layer diffusion = × 100 = 29.40 %
5432.26
 τreaction
alone
Resistance to chemical reaction = × 100
τtotal

3834.81
∴ Resistance to chemical reaction = × 100 = 70.60 %
5432.26

τreaction 3834.81
Relative megnitude of resistances = = = 2.4
τash 1597.45

∴ τreaction = 2.4 τ ash

alone alone

Example: The reduction of iron ore of density B = 4.6 gm/cm3 and

size R = 5-mm by hydrogen can be approximated by the unreacted
core model. With no water vapour present, the stoichiometry of
reaction is
4H2(g) + Fe3O4(s)  4H2O(g) + 3Fe(s)
The rate of reaction approximately proportional to the concentration
of hydrogen in the gas stream. The first order rate has been measured
by Otake et al. (1967) to be
−24000
5
𝑘𝑠 = 1.93 × 10 𝑒 𝑅𝑇 𝑐𝑚/𝑠𝑒𝑐
(a) Taking De = 0.03 cm2/sec as the average value of the diffusion
coefficient for hydrogen penetration of the product layer, calculate
the time necessary for complete conversion of a particle from oxide
to metal at 600 oC. (b) Does any particular resistance control? If not,
what is the relative importance of the various resistance steps?

Solution: From given information, no water vapour present during the

reduction of iron ore, film resistance can safely be neglected as long as
a growing ash layer is present. Reduction of iron ore produce non-
flaking metal as a product that confirm the presence of ash layer.
Finally, the resistance to ash layer diffusion and chemical reaction acts
in series during the reaction.
From given data, particle size R = 5-mm = 0.5-cm, density of solid  =
4.6 gm/cm3  B = 4.6/232 = 0.02 mol/cm3, De = 0.03 cm2/sec, from
reaction stoichiometry of reaction b = 1/4, T = 600 oC = 973 K.

(a) Since pure hydrogen is used in reaction at 900 oC. The volume of 1
mole of hydrogen at 600 oC is

600 + 273
V = 22.4 × = 71.63 liters = 716300 cm3
273

The concentration of hydrogen is

1 gmol
CAg = = 1.396 × 10−5
716300 cm3

The time needed for complete conversion of a particle when diffusion

through ash layer controls alone is calculated as

ρB R2
τ ash =
alone 6 b De CAg

0.02 × (0.5)2
∴τ ash =
1
alone 6× × 0.03 × 1.396 × 10−5
4

∴τ ash = 7959.24 sec = 2.21 h

alone

The first order rate has been measured by

−24000
5
k s = 1.93 × 10 e RT cm/sec

−24000
5
∴ k s = 1.93 × 10 e 1.987 × 873

∴ k s = 1.93 × 105 e−13.8356

 ∴ k s = 1.93 × 105 × 9.80 × 10−7

cm
∴ k s = 0.1891
sec

The time needed for complete conversion of a particle when resistance

to chemical reaction controls alone is calculated as

ρB R
τreaction =
alone b k s CAg

0.02 × 0.5
∴ τreaction =
1
alone × 0.1891 × 1.396 × 10−5
4

∴ τreaction = 15152.45 sec = 4.2090 h

alone

The time needed for complete conversion of a particle when both

diffusion through ash layer and chemical reaction control is

τtotal = τ ash + τreaction = 7959.24 + 15152.45 = 23111.69 sec

alone alone

τ ash
alone
(𝐛) Resistance to ash layer diffusion = × 100
τtotal

7959.24
∴ Resistance to ash layer diffusion = × 100 = 34.43 %
23111.69

τreaction
alone
Resistance to chemical reaction = × 100
τtotal

15152.45
∴ Resistance to chemical reaction = × 100 = 65.57 %
23111.69
 τreaction 15152.45
Relative megnitude of resistances = = = 1.90
τash 7959.24

∴ τreaction = 1.90 τ ash

alone alone

From the relative magnitude of resistance to ash layer diffusion and

resistance to chemical reaction, we can say that no individual resistance
can control the reaction but both resistances may simultaneously
control the reaction.

Example: Two small samples of solids are introduced into a constant

environment oven and kept there for one hour. Under these
conditions, the 4-mm particle are 58% converted and the 2-mm
particles are 87.5% converted.

(a) Find the rate controlling mechanism for the conversion of solids.

(b) Find the time needed for complete conversion of 1-mm particles
in this oven.

Solution: (a) Consider uniform size of particle in each sample and 1 &
2 represent smaller and larger size particle in sample.

From given data, t = 1 h, X1 = 87.5% = 0.875 and X2 = 58% = 0.58

Assume that diffusion through gas film controls, we have

t
= XB
τ
For 2-mm particle

t t 1
= X1 ⟹ τ1 = = = 1.142 h
τ1 X1 0.872

For 4-mm particle

 t t 1
= X 2 ⟹ τ2 = = = 1.72 h
τ2 X 2 0.58
Now
τ2 1.72 R 2 1.5 4 1.5
= = 1.5 and ( ) = ( ) = 2.282
τ1 1.142 R1 2

1.5
τ2 R
≠ ( 2)
τ1 R1
The diffusion through gas film is not a controlling mechanism.

Assume that diffusion through ash layer controls, we have

t 2
= 1 + 2(1 − X B ) − 3(1 − X B ) 3
τ

For 2-mm particle

t 2
( ) ( )
= 1 + 2 1 − X1 − 3 1 − X1 3
τ1

1 2
∴ = 1 + 2(1 − 0.875) − 3(1 − 0.875) 3 = 0.5
τ1

1
∴ τ1 = = 2h
0.5
For 4-mm particle

t 2
= 1 + 2(1 − X 2 ) − 3(1 − X 2 ) 3
τ2

1 2
( ) ( )
∴ = 1 + 2 1 − 0.58 − 3 1 − 0.58 3 = 0.157
τ2

1
∴ τ2 = = 6.349 h
0.157
Now
 τ2 6.349 R2 2 4 2
= = 3.1745 and ( ) = ( ) =4
τ1 2 R1 2

τ2 R2 2
≠ ( )
τ1 R1

The diffusion through ash layer is not controlling mechanism.

Assume that resistance to chemical reaction controls, we have

t 1
= 1 − (1 − X B ) 3
τ

For 2-mm particle

t 1
( )
= 1 − 1 − X1 3
τ1

1 1
∴ = 1 − (1 − 0.875) 3 = 0.5
τ1

1
∴ τ1 = = 2h
0.5

For 4-mm particle

t 1
= 1 − (1 − X 2 ) 3
τ2

1 1
∴ = 1 − (1 − 0.58) 3 = 0.2511
τ2

1
∴ τ2 = = 3.9824 ≅ 4 h
0.2511
Now
τ2 4 R2 4 τ2 R2
= = 2 and = =2 ⟹ =
τ1 2 R1 2 τ1 R1

The resistance to chemical reaction is controlling mechanism.

(b) The resistance to chemical reaction is controlling mechanism

τ ∝R

The time needed for complete conversion of 2-mm and 4-mm particles
are 2 hours and 4 hours respectively, so that the time needed for
complete conversion of 1-mm particles in this oven is 1 hour.

Example: An instantaneous reaction takes place between gas A and

spherical solid B giving rise to a hot solid product S and gaseous
product R. The rate of consumption of A is same as that of formation
of R. Assume that reaction is reversible and gas film resistance is
negligible. Show that flux of gas A through the exterior surface of
solid is:
𝐷𝑒 𝑟𝑐 (𝐶𝐴𝑔 − 𝐶𝐴𝑒 )
𝑄𝐴𝑠 =
𝑅 (𝑅 − 𝑟𝑐 )

where De is diffusivity of gas A through solid, CAg & CAe are bulk and
equilibrium concentration of gas A respectively, R & rc are radius of
solid particle and unreacted core respectively. How does above
equation is simplified when reaction is goes to completion?

Solution: The rate of reaction of A at any instant is given by its rate of

diffusion through ash layer to the reaction surface as

dNA
− = 4πr 2 Q A = 4πR2 Q As = 4πrc2 Q Ac … (1)
dt

The flux of A within the ash layer be expressed by Fick's law for
equimolar counter diffusion as

dCA
Q A = De … (2)
dr
where De is the effective diffusion coefficient of gaseous reactant in the
ash layer. From equations (1) and (2)

dNA dCA
− = 4πr 2 De
dt dr

dNA dr
∴− = 4 π De dCA
dt r 2

Integrating above equation across the ash layer i.e. at rc = R, CA = CAg

= CAs and at rc = rc, CA = CAe

dNA rc dr CAe
− ∫ = 4 π De ∫ dCA
dt R r 2 CAg =CAs

dNA −1 rc
∴− { } = 4 π De (CAe − CAg )
dt r R

dNA 1 1
∴− { − } = 4 π De (CAg − CAe )
dt rc R

dNA 1 1
∴− { − } = 4 π De (CAg − CAe )
dt rc R

dNA R − rc
∴− { } = 4 π De (CAg − CAe )
dt R rc

dNA 4 π De R rc (CAg − CAe )

∴− = … (3)
dt R − rc

From equations (1) and (2)

4 π De R rc (CAe − CAg )
4πR2 Q As =
R − rc
 De rc (CAe − CAg )
Q As =
R (R − rc )

As reaction goes on completion, rc → 0 ⟹ R − rc → R and above

equation reduced to the form

De rc (CAe − CAg )
Q As =
R2

Example: On doubling the particle size from R to 2R, the time for
complete conversion triples. What is the contribution of ash diffusion
to the overall resistance for particles of size R and 2R?

Solution: The time required for complete conversion of particle

neglecting resistance offered by gas film is given by the equation

τtotal = τ ash + τreaction

alone alone

From above equation for particle size of R, we have

∴ τ1 = P + Q … (1)

where τtotal = τ1 ; τ ash = P and τreaction = Q

alone alone

and for particle size of 2R

∴ τ2 = A + B … (2)

where τtotal = τ2 ; τ ash = A and τreaction = B

alone alone

The time required for complete conversion is related to particle size for
ash layer diffusion and chemical reaction control alone by the equations
 τ ash ∝ R2 and τreaction ∝ R
alone alone

From above equation for particle size of R, we find

P ∝ R2 and Q ∝ R … (3)

and for particle size of 2R

A ∝ (2R)2 and B ∝ 2R … (4)

From equations (3) and (4)

A (2R)2 B 2R
= = 4 and = =2
P R2 Q R

∴ A = 4P and B = 2Q … (5)

From equations (2) and (5), the time required for complete conversion
of particle of size 2R is
τ2 = A + B

∴ τ2 = 4P + 2Q … (6)

Given that on doubling the particle size from R to 2R, the time for
complete conversion triples
τ2 = 3 τ1

∴ 4P + 2Q = 3 (P + Q)

∴P=Q

Resistance to ash layer diffusion for particle size of R is

τ ash
alone P P
× 100 = × 100 = × 100 = 50 %
τ1 P+Q 2P
The contribution of ash layer diffusional resistance to the overall
resistance of reaction for particle size of R is 50%.

Resistance to ash layer diffusion for particle size of 2R is

τ ash
alone A 4P
× 100 = × 100 = × 100
τ2 A+B 4P + 2Q

4P
= × 100 [∴ P = Q]
4P + 2P

4P
= × 100 = 66.67%
6P

The contribution of ash layer diffusional resistance to the overall

resistance of reaction for particle size of 2R is 66.67%.

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