FLUID – PARTICLE

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REACTIONS: KINETICS
NON CATALYTIC SYSTEM
MATERIAL INTRODUCTION OF FLUID-PARTICLE
REACTIONS: KINETICS
SELECTION OF A MODEL
SHRINKING-CORE MODEL
FOR SPHERICAL PARTICLES OF
UNCHANGING SIZE
RATE OF REACTION FOR SHRINKING SPHERICAL P
EXTENSIONS
DETERMINATION OF THE RATE-
CONTROLLING STEP
 INTRODUCTION OF
FLUID-PARTICLE
REACTIONS: KINETICS
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
 As shown in Fig. 25.1, solid particles remain unchanged in size
during reaction when they contain large amounts of impurities which
remain as a nonflaking 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.
SELECTION OF
A MODEL
 We should clearly understand that every conceptual picture or model
for the progress of reaction comes with its mathematical representation, its
rate equation. Consequently, if we choose a model we must accept its rate
equation. If a model corresponds closely to what really takes place, then its
rate expression will closely predict and describe the actual kinetics, If a
model differs widley from reality, then its kinetic expressions will be
useless.
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. 25.2.
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. 25.3.
SHRINKING-CORE
MODEL
FOR SPHERICAL
PARTICLES OF
UNCHANGING SIZE
 STEPS 1 Diffusion of gaseous reactant A through the
film surrounding the particle to the surface
A + B -> Solid of the liquid
Penetration and diffusion of A through the
+ Gas 2
blanket of ash to the surface of the
unreacted core
3 Reaction of gaseous A with solid at this
reaction surface

4 Diffusion of gaseous products through the

ash back to the exterior surface of the solid

5 Diffusion of gaseous products though the

gas film back into the main body of fluid
 A
A STEP 15 A
A A
A A A A
STEP 42
Spt Spt
A A STEP 3 A A
Spt Spt
B
GptSpt
A B B A
Spt Spt

B B
B B
HOW DO WE DETERMINE THE
RATEDIFFUSION
OF REACTION ?
THROUGH
GAS FILM
CONTROL
DIFFUSION
THROUGH
ASH LAYER
CONTROL
CHEMICAL
REACTION
CONTROL
DIFFUSION
THROUGH
GAS FILM
CONTROL
DIFFUSION
THROUGH
ASH LAYER
CONTROL
CHEMICAL
REACTION
CONTROL
RATE OF REACTION
FOR SHRINKING
SPHERICAL
PARTICLES
 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. 25.8. For a reaction of this kind we
visualize the following three steps occurring in succession.
1 Diffusion of reactant A from the main body of gas through the gas
film to the surface of the solid.
2 Reaction on the surface between reactant A and solid.
Diffusion of reaction products from the surface of the solid
3 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.
Chemical Reaction Controls
When chemical reaction controls, the behavior is identical to that of
particles of unchanging size. It’s depend only on unreacted core.

The figure and equation will

represent the conversion-time
behavior of single particles, both
shrinking and of constant size.
 • Gas Film Diffusion Controls
Film Resistance is dependence to several
factors:
- Relative velocity between particle and
fluid
- Size
Kgof particleFroessling
- Fluid properties

 For small dp & u Stokes law can be applied

 For large dp & u

• Stokes Regime ( for small
particle
1 )

2Then, analogous to eq 7, we have :

3 For Complete reaction  R=0

4
EXTENS
IONS
• Particles of Different Shape
Conversion-time equations similar to those developed above can be obtained
for various-shaped particles, and Table 25.1 summarizes these expressions
 • Combination of Resistances

 In an alternative approach, the individual resistances can be combined directly to

give, at any particular stage of conversion

 On aconsidering 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

 For ash-free particles which shrink with reaction

• Limitations of the Shrinking Core Model
 The assumptions of this model may not match reality precisely
 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.
 Shrinking core model is the best simple representation for the majority of
reacting gas-solid systems [Wen(1968) and Ishida et al.(1971)] .
 Therefore it has 2 exceptions for this conclusion:
1 . Slow reaction of a gas with a very porous solid
2. Solid is converted by the action of heat, and without needing contact
with gas.
DETERMINATION
OF
THE RATE-
CONTROLLING
STEP
 The kinetics and rate-controlling steps of a fluid-solid reaction are
deduced by noting how the progressive conversion of particles is
influenced by particle size and operating temperature. This information
can be obtained in various ways, depending on the facilities available
and the materials at hand. 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
Figures 25.9 and 25.10 show the progressive conversion of spherical solids when
chemical reaction, film diffusion, and ash diffusion in turn control. 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.
• Particle Size
for unchanging sizes is given by

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 nonflaking 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 Eq. 24. Thus an observed rate
approximately equal to the calculated rate
suggests that film resistance controls.
• Overall Versus Individual Resistance
The overall coefficient given by Eq. 34 or 35 cannot be higher than any of the individual
coefficients. So, let us illustrate the interplay of resistances with the well-studied gas-
solid reaction of pure carbon particles with oxygen.

Since no ash is formed at any time during reaction, we have here a case of kinetics of
shrinking particles for which two resistances at most, surface reaction and gas film,
may play a role. In terms of these, the overall rate constant at any instant from Eq. 35
is
 Figure 25.12 shows all this information in convenient
graphical form and allows determination of k" for different
values of the system variables. Note that when film resistance
controls, the reaction is rather temperature insensitive but
is dependent on particle size and relative velocity between
solid and gas. This is shown by the family of lines, close to
parallel and practically horizontal.
In extrapolating to new untried operating
conditions, we must know when to be prepared for a change
in controlling step and when we may reasonably expect the
rate-controlling step not to change. For example, for particles
with nonflaking ash a rise in temperature and to a lesser extent
an increase in particle size may cause the rate to switch from
reaction to ash diffusion controlling. For reactions in which
ash is not present, a rise in temperature will cause a shift
from reaction to film resistance controlling.
THANK
………
YOU