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Two cases
1. Solid particles contain large amount of inert material which remain as a non-flaking ash or
2. A firm product material is formed by the reactions.
Example
Kinetic models
The closest representation of reality which can be treated without too many mathematical complexities
The reactant gas enters and reacts throughout the particle at all times , most likely at different
rates at different locations within the particle.
The solid reactant is converted continuously and progressively throughout the particle
Shrinking Core Model (SCM)
Assumption
The reaction first begins 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 reaction zone then moves inward (into the solid), constantly reducing the
size of core of unreacted solid and leaving behind completely converted solid (solid product) and
inert material (inert constituent of the solid reactant).
1. Diffusion of gaseous reactant A through the gas film surrounding the particle to the surface of
solid particle – External diffusion.
2. Penetration of A by diffusion through pores and cracks in the blanket (layer) of ash to the surface
of the unreacted core – pore or internal diffusion.
3. Reaction of gaseous reactant A with solid B at the surface of the unreacted core – reaction
surface.
4. Diffusion of any gaseous products back to the exterior surface of solid through the ash (ash layer)
– reverse internal diffusion.
5. Diffusion of gaseous products through the gas film back in to the main body of gas – reverse
external diffusion.
The rate of reaction of A per unit surface = The molar flux of A from the main body of gas to the
surface of the particle.
The eqn. (12) is represents the relationship of time with the radius of unreacted core and
fractional conversion of B
The above eqn. gives an idea regarding the progress of reaction in terms of the time
required for complete conversion.
When no ash forms, as in the burning of pure carbon in the air, the reacting particle shrinks
during reaction, finally disappearing.
Diffusion of reactant A from the main body of gas through the gas film to the solid surface
surface.
Reaction on the surface b/w reactant A and solid.
Diffusion of reaction products from the surface of the solid through the gas film back into the ain
body of gas. Note that the ash layer is absent and does not contribute any resistance.
Here the rate controlling step may be gas film diffusion or chemical reaction
The expressions derived for single particles of unchanging size are directly applicable to the shrinking
spherical particles (changing size) when chemical reaction controls the overall rate of reaction.
Diffusion through gas film controls
The above eqn. expresses the relationship of size with time for shrinking particles in the Stokes regime.
This eqn. well represents small burning solid particles as well as small burning liquid droplets
SCM for Cylindrical particles of Unchanging size/Fixed size (Radius R and Length L)
Contacting patterns
Gas passes through a stationary bed of solids, charged and removed batch wise.
Approximates plug flow, used for small scale operations
Ex- ion-exchange column.
Batch operations
Mixture of Particles of Different but Unchanging Sizes, Plug Flow of Solids, Uniform Gas
Composition
Let F(R,) be the quantity of material of size about Ri fed to the reactor.
If R, is the largest particle size in the feed, we have for particles of unchanging size
When in plug flow all solids stay in the reactor for the same length of time tp
The conversion XB(Ri) for any size of particle Ri can be found.
Mixed Flow of Particles of a Single Unchanging Size, Uniform Gas Composition
Fluidized bed reactor with constant flow rates of both solids and gas into and out of the reactor.
Assumption
Uniform gas concentration and mixed flow of solids, this model represents a fluidized-bed reactor
in which there is no elutriation of fine particles.
The conversion of reactant in a single particle depends on its length of stay in the bed, and its
appropriate controlling resistance.
However, the length of stay is not the same for all the particles in the reactor; hence we must
calculate a mean conversion, XB of material.
The solids leaving the reactor
For mixed flow of the single size of solid which is completely converted in time, we obtain
Rate controlling steps
Film resistance controls