Unit 3

CHEMICAL REACTIONS ENGINEERING II (3170501)
Semester – VII (CHEM)

CHAPTER: 3
Chapter Name: Fluid-Particle System
3.1 INTRODUCTION
This chapter deals with the kinetics of fluid-particle reactions - non-catalytic
heterogeneous in which a gas or liquid is brought in contact with a solid and reacts with
the solid to transform (convert) it into a product. Fluid-particle reactions yield fluid and/or
solid products and thus may be represented by
A (fluid) + bB (solid)  Fluid products … (4.1)

 Solid products … (4.2)
 Fluid and solid products … (4.3)
In case of such reactions, we have two different cases to consider:
1. The particle size remains unchanged during the reaction. In fluid-solid reactions
this will happen when –
(a) Solid particles contain large amount of inert material, which remain as a non-
flaking ash.
(b) A firm product material is formed by the reactions of Solid products or Fluid
and solid products
Examples of fluid-solid reactions in which the solid does not appreciably change in
size during reaction are :
(i) The roasting of sulphide ores in air to yield the metal oxides. For example, zinc
sulphide is roasted to produce zinc oxide.
ZnS (s) + O2 (g) → ZnO (s) + SO2 (g)
(ii) The reduction of metal oxides to the corresponding metals. For example,
reduction of magnetite, Fe3O4, by hydrogen occurs according to the following
reaction to produce iron.
Fe3O4 (s) + 4H, (g)  3Fe (s) + 4H2O(g) 4
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2. The particle size changes with the progress of reaction (the particle decreases in
size, Shrinks during the course of reaction until it disappears).
 In fluid-particle reactions this will happen when -
(a) A flaking ash or product material is formed or
(b) Pure B is used in the reaction of Fluid products
 Examples of fluid-solid reactions in which the size of solid changes are :
(i) The production of carbon disulphide from the elements:
C(s) + 2S (g) → CS2 (g)
(ii) The production of water gas by the action of steam on coal (with low ash content).
C (s) + H20 (g) → CO (g) + 2H(g)
(iii) The burning of pure carbon in air :
C(s) + O2 (g) + CO2(g)
3.2 SELECTION OF KINETIC MODEL

 Every conceptual picture or model describing the progress of reaction has its own
mathematical representation, its rate equation.
 Therefore, if we select a model we have to accept its rate equation and vice versa. If a
model matches closely with what really happens, then its rate equation will closely
predict and describe the actual kinetics of the reaction, whereas differs widely from
what really happens, then its rate equation will be useless.
 It is Worthless to select a model, which involves too many mathematical complexities
even though very close it reflects/represents reality.
 One has to select a model which is the closest representation of reality and at the same
time it should be easy to treat mathematically (i.e., the kinetic models selected can be
described with relatively simple equations).

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 Many kinetic models have been developed for the progress of the reaction within a
single solid particle. To describe the progress of the non-catalytic reaction of particles
with surrounding fluid, we consider two simple models regarded as perfect in reality,
namely the progressive Conversion model and the shrinking unreacted - core model.
3.3 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.
3.4 SHRINKING - CORE MODEL (SCM):

 This model assumes that reaction begins first at the outer surface of the solid particle
and the deeper layers do not take part in the reaction until all the outer layer has
transformed into solid or gaseous product. Gradually, the reaction zone then moves
inward (into the solid), constantly reducing the size of core of the unreacted solid and
leaving behind completely converted solid (solid product) and inert material (inert
constituent of the solid reactant).

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 We define converted solid (i.e., solid product) and inert material as ash. An unreacted
core of solid continuously decreases in size / shrinks in size during reaction until it is
entirely consumed (Here the amount of solid material to be consumed by reaction is
shrinking with time)
 At any given instant, the solid particle comprises of a core surrounded by an envelope.
The core is the unreacted reactant (that shrinks with time) so this model is referred to
as shrinking unreacted-core model. The envelope consists of a solid product and inert
material. The shrinking of size of unreacted core of solid with reaction time is shown
in Fig.
 As the shrinking - core model (SCM) has been reported to approximate closely a
number of fluid - solid reactions, let us develop its kinetic equations for fixed as well
as variable se particles.
 In doing this, we consider the surrounding fluid to be a gas spherical particles and
irreversible reaction between a gas and a solid
 Please note that in the analysis to follow we consider the surrounding fluid a gas but
keep in mind that the analysis given below is applicable equally well to liquids.

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 Comparison of Models with Real Situations.

 In slicing and examining the cross section of partly reacted solid particles, we usually
find unreacted solid material surrounded by a layer of ash.
 The boundary of this unreacted always be as sharply defined as the model pictures it;
nevertheless, evidence from a wide variety of situations indicates that in most cases
the shrinking-core model (SCM) approximates real particles more closely than does
the progressive conversion model (PCM).
 Observations with burning coal, wood, briquettes, and tightly wrapped newspapers
also favor the shrinking-core model.
 Since the SCM seems to reasonably represent reality in a wide variety of situations,
we develop its kinetic equations in the following section. In doing this we consider
the surrounding fluid to be a gas. However, this is done only for convenience since
the analysis applies equally well to liquids.
3.5 SHRINKING - CORE MODEL (SCM) FOR SPHERICAL PARTICLES OF

UNCHANGING SIZE / FIXED SIZE:
 According to this model, the following five steps occur in succession during reaction
(i) Diffusion of gaseous reactant A through the gas film surrounding the particle to
the surface of the solid particle ... reactant A diffuses to the external surface or particle
from the bulk gas phase through the gas film ...... external diffusion.
ii) Penetration of A by diffusion through pores and cracks in the blanket (layer) 01 -
the surface of the unreacted core ... pore or internal diffusion.
(iii) Reaction of gaseous A with solid B at the surface of the unreacted core (reaction
surface).
(iv) Diffusion of gaseous products back to the exterior surface of the solid through the
sun (ash layer) ... reverse internal diffusion.
(v) Diffusion of gaseous products through the gas film back into the main body of gas
... reverse external diffusion.
 Fig. shows the concentration profile of a gaseous reactant A reacting with a solid
particle the concentration of reactant A at different points of the reaction space.
 In all gas-solid reactions, all these steps may not exist. If no gaseous products are
formed, Steps (iv) and (v) do not exist and thus do not contribute to the resistance to
reaction.

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 All these steps offer resistance to reaction and the magnitude of the resistances of
these steps usually differ greatly from each other. In such cases, the step with the
highest resistance is considered as the rate - controlling / rate - determining for the
overall reaction process.
 One of the following three steps may control the overall reaction rate. Therefor
develop the conversion equations for spherical particles by considering each of the
steps separately to be rate controlling.
(i) Diffusion through the gas film.
(ii) Diffusion through the ash (converted solid and inert material) / ash layer.
(iii) Chemical reaction.

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3.9 RATE OF REACTION FOR SHRINKING SPHERICAL PARTICLES

(VARIABLE / CHANGING PARTICLE SIZE)
 When no ash (converted solids and inert material) forms (no ash layer cover the
unreacted core as the reaction proceeds), the reacting particle continuously shrinks in
size with time during reaction until it disappears.
 This process is illustrated in Fig.
 In case of such reactions as no ash layer is present, the following three step occur in
succession/series :
(i) Diffusion of gaseous reactant A through the gas film to the surface of the solid
- from the main body of gas.
(ii) Reaction on the surface between gaseous reactant A and solid reactant B.
(iii) Diffusion of reaction products from the surface of the solid back into the main
body of gas through the gas film.
 Here the rate-controlling step may be gas film diffusion or chemical reaction

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3.10 CHEMICAL REACTION CONTROLS (CONTROLLING RESISTANCE-

REACTION STEP):
The expressions derived for t, τ and XB-t for single particles of unchanging size are
directly applicable to the shrinking spherical particles (spherical particles of changing
size) when chemical reaction step controls the overall rate of reaction.
3.11 DIFFUSION THROUGH GAS FILM CONTROLS (CONTROLLING

RESISTANCE-FILM DIFFUSION):
 When diffusion through the gas film controls, the situation becomes more
complicated because of the changing particle size in turn changing the film resistance.
Film resistance at the surface of a particle depends upon the following parameters:
(i) Size of particle,
(ii) Properties of fluid,
(iii) Relative velocity between particle and solid.
 These parameters have been correlated for various ways of contacting fluid with solid.
The correlation for mass transfer of a component with mole fraction y in a fluid to
free-falling solids is:

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PARTICLES OF DIFFERENT SHAPE : Conversion-time equations similar to those

developed above can be obtained for various-shaped particles, and Table summarizes
these expressions.

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LIMITATIONS OF THE SHRINKING CORE MODEL.

 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.
 Also, 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. There are, however, two broad classes of exceptions to this
conclusion.
o 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.
o 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.
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 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 ratecontrolling 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.

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 Particle Size. The time needed to achieve the same fractional conversion for
particles of different but 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. 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, the overall coefficient cannot be higher
than any of the individual coefficients.
Figure: 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.

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QUESTION NUMBER 1 OF QUESTION BANK

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QUESTION NUMBER 2 and 6 OF QUESTION BANK

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QUESTION NUMBER 5 and 8 OF QUESTION BANK

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CHEMICAL REACTIONS ENGINEERING II (3170501)

Semester – VII (CHEM)

A (fluid) + bB (solid)  Fluid products … (4.1)

ZnS (s) + O2 (g) → ZnO (s) + SO2 (g)

3.2 SELECTION OF KINETIC MODEL

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3.3 PROGRESSIVE - CONVERSION MODEL (PCM)

3.4 SHRINKING - CORE MODEL (SCM):

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 Comparison of Models with Real Situations.

3.5 SHRINKING - CORE MODEL (SCM) FOR SPHERICAL PARTICLES OF

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3.9 RATE OF REACTION FOR SHRINKING SPHERICAL PARTICLES

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3.10 CHEMICAL REACTION CONTROLS (CONTROLLING RESISTANCE-

3.11 DIFFUSION THROUGH GAS FILM CONTROLS (CONTROLLING

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PARTICLES OF DIFFERENT SHAPE : Conversion-time equations similar to those

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LIMITATIONS OF THE SHRINKING CORE MODEL.

DETERMINATION OF THE RATE-CONTROLLING STEP

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QUESTION NUMBER 1 OF QUESTION BANK

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