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Fluid-Particle Reactions-Kinetics
FLUID-PARTICLE
REACTIONS: KINETICS
NAA©2015
Fluid-Particle Reactions-Kinetics
• These are heterogeneous reactions
in which a gas or solid reacts with a
solid and transforms it into a product
• Can be represented in the following
forms:
Fluid-Particles Reactions
Reactions between:
Liquid-Solid
Non catalytic (no catalyst)
Gas-Solid
Fluid-Particle Reactions-Kinetics
Particles of unchanging size:
• Solid particles containing large amounts of
impurities remain unchanged in size during
reaction and exists as a non flaking ash
• For reactions producing solid products, the
solid reacting particles forms a firm solid
material which retains its size
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Fluid-Particle Reactions-Kinetics
Particles of unchanging size:
• 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
– The roasting (or oxidation) of sulfide ores to yield
the metal oxides. For example, in the preparation
of zinc oxide the sulfide 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
Fluid-Particle Reactions-Kinetics
Particles of changing size:
• Particles shrink in size during reaction when a
flaking ash or product material is formed
especially for the case of fluid products
• This can also happen when pure B is used in
the reaction
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Fluid-Particle Reactions-Kinetics
Particles of unchanging size:
– 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-countercurrent, three-stage,
fluidized-bed reactors according to the reaction
– The nitrogenation of calcium carbide to produce
cyanamide
– The protective surface treatment of solids such as
the plating of metals
Fluid-Particle Reactions-Kinetics
Particles or changing size:
• 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. Others include:
– The manufacture of carbon disulfide from the elements
– The manufacture of sodium cyanide from sodium amide
– The manufacture of sodium thiosulfate from sulfur and
sodium sulfite
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Fluid-Particle Reactions-Kinetics Fluid-Particle Reactions-Kinetics

Selection of a Model:
• Every conceptual picture or model for the
progress of a reaction comes with its
mathematical representation which is 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
• The requirement for a good engineering
model is that it be the closest representation
of reality which can be treated without too
many mathematical complexities
Selection of a Model:
• For the noncatalytic reaction of
particles with surrounding fluid, we
consider two simple idealized models
–The progressive-conversion model
(PCM)
–The shrinking unreacted-core model
(SCM)

Fluid-Particle Reactions-Kinetics Fluid-Particle Reactions-Kinetics

Progressive-Conversion • Solid reactant is converted Shrinking Core Model • At any time there exists an
Model (PCM) continuously and (SCM) unreacted core of material
• Reactant gas enters and progressively throughout • Reaction occurs first at which shrinks in size
reacts throughout the the particle as shown the outer skin of the during reaction, as shown
particle at all times particle
• Likely at different rates • The zone of reaction
at different locations then moves into the
within the particle solid, leaving behind
completely converted
solid inert material
referred to as ash

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Fluid-Particle Reactions-Kinetics Fluid-Particle Reactions-Kinetics

Comparison of model with real situation:
• When a cross section of partly reacted solid
particles is sliced and examined, we usually find
unreacted solid material surrounded by a layer of
ash
• The boundary of this unreacted core may not
always be as sharply defined as the model
pictures it
• However, 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)
Comparison of model with real situation:
• 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

Fluid-Particle Reactions-Kinetics Fluid-Particle Reactions-Kinetics

SCM for spherical particles of unchanging size SCM for spherical particles of unchanging size
• Step 1: Diffusion of
gaseous reactant A
• First developed through the film
by Yagi and Kunii surrounding the particle
(1955, 1961) to the surface of the
solid
• Conceptualized • Step 2: Penetration and
in five steps diffusion of A through
occurring in the blanket of ash to the
surface of the unreacted
succession core
during reaction • Step 3: Reaction of
gaseous A with solid at
this reaction surface

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Fluid-Particle Reactions-Kinetics Fluid-Particle Reactions-Kinetics

SCM for spherical particles of unchanging size SCM for spherical particles of unchanging size
• Step 4: Diffusion of • In some situations some of these steps do not exist
gaseous products • For instance, if no gaseous products are formed,
through the ash steps 4 and 5 do not contribute directly to the
resistance to reaction
back to the exterior
• Also, the resistances of the different steps usually
surface of the solid
vary greatly one from the other
• Step 5: Diffusion of • In such cases we may consider that step with the
gaseous products highest resistance to be rate-controlling
through the gas film • We shall then develop the conversion equations for
back into the main spherical particles in which steps 1, 2, and 3, in turn,
body of fluid are rate-controlling

Fluid-Particle Reactions-Kinetics Fluid-Particle Reactions-Kinetics

SCM-Unchanging size: Diffusion Through Gas Film Controls SCM for spherical particles of unchanging size
• When the resistance of • The kinetic expressions will be derived based on
the gas film controls, the
concentration profile for
the unchanging exterior surface of a particle Sex
gaseous reactant A will • Noting from the stoichiometry of the equations:
be shown
• No gaseous reactant is
present at the particle
surface
• The concentration driving
force, CAg - CAs becomes
CAg and is constant at all
times during reaction of
the particle (4)

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Fluid-Particle Reactions-Kinetics
SCM for spherical particles of unchanging size
• If we let ρB 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: (5)
• The decrease in volume or radius of unreacted
core accompanying the disappearance of dNB
moles of solid reactant is then given by:
(6)
Fluid-Particle Reactions-Kinetics
SCM for spherical particles of unchanging size
(7)
• Rearranging and integrating, we find how the
unreacted core shrinks with time
(8)
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Fluid-Particle Reactions-Kinetics
SCM for spherical particles of unchanging size
• Replacing Eq. 6 in 4 gives the rate of reaction in
terms of the shrinking radius of unreacted core
(4)
(6)
(7)
• kg is the mass transfer coefficient between fluid
and particle
Fluid-Particle Reactions-Kinetics
SCM for spherical particles of unchanging size
• If the time for complete conversion of a particle is
taken as τ, at complete conversion, rc=0 such that:
(9)
• The radius of unreacted core in terms of
fractional time for complete conversion is
obtained by combining (8) and (9):
(10)
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Fluid-Particle Reactions-Kinetics Fluid-Particle Reactions-Kinetics

SCM for spherical particles of unchanging size SCM-Unchanging size: Diffusion Through Ash layer Controls
• This can be written in terms of fractional • Considering the Figure,
conversion by noting that: Both reactant A and the
boundary of the
unreacted core move
inward toward the center
(10) of the particle
• Therefore: • The rate of reaction of A
at any instant is given by
its rate of diffusion to the
(11) reaction surface
This shows the relationship of time with radius and
(12)
with conversion when gas film resistance controls

Fluid-Particle Reactions-Kinetics Fluid-Particle Reactions-Kinetics

SCM-Unchanging size: Diffusion Through Ash layer Controls SCM-Unchanging size: Diffusion Through Ash layer Controls
• The flux of A within the ash layer can be expressed by
Fick's law for equimolar counterdiffusion i.e. (15)
(13) • Recall equation (6)
(6)
• Combining Eqs. 12 and 13, we obtain for any r:
• Combining Eqs. 6 and 15, separating variables, and
(14)
integrating we obtain:

• Integrating across the ash layer form R to rc, we obtain:

(15)
(16)
This expression represents the conditions of a reacting particle at any time

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Fluid-Particle Reactions-Kinetics Fluid-Particle Reactions-Kinetics

SCM for spherical particles of unchanging size SCM-Unchanging size: Chemical reaction Controls
• If the time for complete conversion of a particle is • progress of the reaction is
taken as τ, at complete conversion, rc=0 such that: unaffected by the presence
of any ash layer
(17)
• The rate is proportional to
• The radius of unreacted core in terms of fractional the available surface of
time for complete conversion is obtained by unreacted core
combining (16) and (17): • The rate of reaction of A at
any instant is given based
(18a) (18b) on unit surface of
unreacted core rc:
(18b) in terms of fractional conversion (19)

Fluid-Particle Reactions-Kinetics Fluid-Particle Reactions-Kinetics

SCM-Unchanging size: Chemical reaction Controls SCM for spherical particles of unchanging size
• k’’ is the first-order rate constant for the surface reaction • If the time for complete conversion of a particle is
• Writing NB in terms of the shrinking radius, as given in Eq. taken as τ, at complete conversion, rc=0 such that:
6, we obtain: (22)
(20) • The radius of unreacted core in terms of
• On integration: fractional time for complete conversion is
obtained by combining (21) and (22):
(23)
(21)
This shows the relationship of time with radius and with
conversion when chemical reaction controls

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Fluid-Particle Reactions-Kinetics
SCM for spherical particles of changing size
• When no ash forms, as in the reaction of pure B
in the fluid phase, the reacting particle shrinks
during reaction, finally disappearing at complete
conversion
Fluid-Particle Reactions-Kinetics
SCM-changing size: Chemical reaction Controls
• When chemical reaction
controls, the behavior is
identical to that of particles
of unchanging size
• The Figure and previously
derived equations will
represent the conversion-
time behavior of shrinking
reacting particles
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Fluid-Particle Reactions-Kinetics
SCM for spherical particles of changing size
The SCM predicts that reactions of this type
proceeds conceptually in three steps
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
The ash layer is absent and does not contribute any
resistance
Fluid-Particle Reactions-Kinetics
SCM-Changing size: Diffusion Through Gas Film Controls
• Film resistance at the surface of a particle is dependent
on numerous factors
– Relative velocity between particle and fluid,
– size of particle
– 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
• For instance the case of mass transfer of a component of
mole fraction y in a fluid to free-falling solids was correlated
by Froessling (1938) as:
(24)
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Fluid-Particle Reactions-Kinetics
SCM-Changing size: Diffusion Through Gas Film Controls
• In the course of the reaction, the size
of the particle changes; hence the
value of kg also varies
• In general kg rises for an increase in
gas velocity and for smaller particles
• Comparing Eq (24) with the Figure
reveals the following:
• y is component mole fraction
• We will develop conversion-time expressions for
particles of Eq (25) which represents the Stokes
law regime
Fluid-Particle Reactions-Kinetics
SCM for spherical particles of changing size:
Stokes law regime (small particles)
• For Stokes law regime, Eq (24) reduces to:
• Combining this with (27) and integrating:
• The time for complete conversion is (R=0):
In terms of conversion
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Fluid-Particle Reactions-Kinetics
SCM for spherical particles of changing size:
Stokes law regime (small particles)
• The kinetic expressions will be derived based on
the unchanging exterior surface of a particle Sex
• At the time when a particle, originally of size Ro
has shrunk to size R, we have:
• With necessary substitutions:
(27)
Fluid-Particle Reactions-Kinetics
Extension of the SCM for other particles
(28) Conversion-time equations similar to
those developed above can be obtained
for various-shaped particles
(29)
(30)
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Fluid-Particle Reactions-Kinetics
Fluid-Particle Reactions-Kinetics
SCM: Combination of resistances
• The resistance to reaction increases as the
surface of unreacted core decreases
• The ash layer resistance is nonexistent at the
start because no ash is present, but becomes
progressively more and more important as the
ash layer builds up
• Thus it may not be reasonable to consider that
just one step controls throughout reaction
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Fluid-Particle Reactions-Kinetics
SCM: Combination of resistances
• The conversion-time expressions developed
previously 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 instance, consider a constant size particle:
the gas film resistance remains unchanged in
the course of the reaction
Fluid-Particle Reactions-Kinetics
SCM: Combination of resistances
• It is necessary to account for the simultaneous
effect of these resistances
• It is quite a straight forward process as the
resistances act in series and are linear in
concentration
• Thus on combining Eqs. (7), (15), and (20) 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
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Fluid-Particle Reactions-Kinetics
SCM: Combination of resistances
• Eqs. (7), (15), and (20)
(7)
(15)
(20)
At any time:
(31a)
For complete conversion:
(31b)
Fluid-Particle Reactions-Kinetics
SCM: Combination of resistances
• 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:
(33)
• For ash-free particles which shrink with
reaction, only two resistances, gas film and
surface reaction, need to be considered
(34)
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Fluid-Particle Reactions-Kinetics
SCM: Combination of resistances
• Alternatively, the individual resistances can be
combined directly to give, at any particular
stage of conversion:
(32a)
(32b)
• The relative importance of the three individual
resistances varies as conversion progresses, or
as rc decreases
Fluid-Particle Reactions-Kinetics
Limitations of the SCM
• The assumptions of the SCM may not match
reality precisely
• For instance, reaction may occur along a diffuse
front rather than along a sharp interface
between ash and fresh solid, thus giving
behavior intermediate between the SCM and
the PCM
• 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
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Fluid-Particle Reactions-Kinetics
Limitations of the SCM
• However, despite these observations, the SCM
is the best simple representation for the
majority of reacting gas-solid 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 PCM may be expected to better fit reality
• An example of this is the slow poisoning of a
catalyst pellet
Fluid-Particle Reactions-Kinetics
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
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Fluid-Particle Reactions-Kinetics
Limitations of the SCM
• 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 mouthwatering examples of such
reactions
Fluid-Particle Reactions-Kinetics
Determination of the rate controlling step
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
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Fluid-Particle Reactions-Kinetics Fluid-Particle Reactions-Kinetics

Determination of the rate controlling step Determination of the rate controlling step
Time:
• The 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 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

Fluid-Particle Reactions-Kinetics Fluid-Particle Reactions-Kinetics

Determination of the rate controlling step Determination of the rate controlling step
Particle size:
• Equations (8), (16), (21) with (24) or (25) show
the time needed to achieve the same fractional
conversion (changing and unchanging size)

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Fluid-Particle Reactions-Kinetics
Determination of the rate controlling step
Particle size:
• These Equations show that 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.
Fluid-Particle Reactions-Kinetics
Example
A batch of solids of uniform size is treated by gas
in a uniform environment. Solid is converted to
give a nonflaking product according to the
shrinking-core model. Conversion is about 7/8 for
a reaction time of 1 h, conversion is complete in 2
h. What mechanism is rate controlling?
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Fluid-Particle Reactions-Kinetics
Determination of the rate controlling step
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
Fluid-Particle Reactions-Kinetics
Solution
The procedure to follow is to test which of the
three SCM mechanisms satisfies the given
information i.e.
XB=7/8=0.875 at t=1 h
XB=1.0 at t=τ=2 h
This means that: t/τ=1/2=0.5
We can assume spherical particles since the shape
of the particles is not specified
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Fluid-Particle Reactions-Kinetics Fluid-Particle Reactions-Kinetics

Solution Solution
Film diffusion resistance: Diffusion through ash layer:
If this is controlling, then: t If this is controlling, then:
= XB
τ
t
= 1 − 3(1 − X B )2/3 + 2(1 − X B )
But t = 1 = 0.5 ≠ 0.875 τ
τ 2

Since the mathematical expressions for this
mechanism doesn’t hold, it implies that it is not
the controlling mechanism
But t = 1 = 0.5 = 1 − 3(1 − 0.875)2/3 + 2(1 − 0.875) = 0.5
τ 2
Since there is agreement, i.e. the mathematical
expression for this mechanism holds, it implies
that it is the controlling mechanism

Fluid-Particle Reactions-Kinetics Fluid-Particle Reactions-Kinetics

Solution Solution
Chemical reaction: Observations:
If this is controlling, then: • The difference between ash diffusion and
chemical reaction as controlling steps is not great
t
= 1 − (1 − X B )1/3 • In this case, there is no difference
τ
• Figs 9 and 10 shows that the data were taken at
t 1 the point of intersection between the ash
But = = 0.5 = 1 − (1 − 0.875)1/3 = 0.5
τ 2 diffusion and chemical reaction mechanisms

Also, since there is agreement, i.e. the mathematical

expression for this mechanism holds, it implies that
it is the controlling mechanism

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Fluid-Particle Reactions-Kinetics Fluid-Particle Reactions-Kinetics

Example Example
In a shady spot at the end of Brown Street in Calculate the time needed to burn to completion
Lewisburg, Pennsylvania, stands a Civil War particles of graphite (Ro=5 mm, ρB=2.2 g/cm3, k”=20
memorial-a brass general, a brass cannon which cm/sec) in an 8% oxygen stream. For the high gas
persistent undergraduate legend insists may still fire velocity used assume that film diffusion does not
some day, and a stack of iron cannonballs. At the offer any resistance to transfer and reaction.
time this memorial was set up, 1868, the Reaction temperature = 900°C
cannonballs were 30 inches in circumference. Today
due to weathering, rusting, and the once-a-decade
steel wire scrubbing by the DCW, the cannonballs
are only 29.75 in. in circumference. Approximately,
when will they disappear completely?

Fluid-Particle Reactions-Kinetics Fluid-Particle Reactions-Kinetics

Solution Solution
Preliminary observations: • When chemical reaction is rate controlling, we
• In this case, we have particles of changing size have: t 1/3
ρ B Ro
= 1 − (1 − X B ) τ=
• Hence only two resistance come into play τ bk " C Ag
(resistance due to the gas film and that due to • The density of graphite expressed in mol/cm3 is given as:
chemical reaction)
2.2 g / cm3
• The question indicates that gas film resistance can ρB = = 0.183mol / cm3
12 g / mol
be neglected
• The concentration of oxygen is given as:
• Hence only one resistance (chemical reaction) is PAg y Ag P
acting C Ag = =
RT RT
• The same expression for unchanging particles
0.08 × 101325
applies C Ag = = 0.831mol / m3 = 8.31 × 10−7 mol / cm3
8.314 × (900 + 273)

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Fluid-Particle Reactions-Kinetics
Solution
• The reaction between graphite and oxygen is:
C + O2 
→ CO2 Hence b=1
• Making necessary substitutions:
• The concentration of oxygen is given as:
0.183 × 0.5
τ=
1 × 20 × 8.31 × 10−7

τ = 5505.4sec = 1.53hrs

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