Gas –Solid Reactions: In the solid gas reaction, a solid reaction product is generally obtained which forms a layer

between the unreacted solid and the reacting gas.

Example: Roasting of sulphide ore, reduction of metal oxide, oxidation of metals in air etc.

Consecutive steps in gas-solid reaction: A metal oxide (MO) (pellet) is

reduced by hydrogen, MO + H2 = M + H2O or FeO + CO = Fe + CO2
In a topochemical model, the reaction front proceeds linearly towards the
centre and the shrinking core of the unreacted material retains the initial
shape of the pellets.
In this the equation given below is valid
𝑑𝑟
𝑛 = 4𝜋𝑟 2 𝜌
𝑑𝑡

Where, 𝑛 is the rate of the reaction (moles/sec)

𝑟 is the radius (cm) of the reaction front and 𝜌 is the molar density (g mole
cm-3)
When gas reacts with a solid three basic steps are involved

Step I: An external mass transfer step involving the diffusion of the reactant
and product through the film boundary layer surrounding the spherical oxide
pellets undergoing reduction.
Step II: The diffusion of the reactant and product gases through the porous solid product layer or the solid-state diffusion
of ions through this layer.
Step III: The adsorption of the gaseous reactant at the reactant surface, chemical reaction at the interface and desorption
of the gaseous product from the solid reactant surface.
I (a) Diffusion of the gaseous reactant through the boundary layer
II (a) Diffusion of the gaseous reactant through the product layer
III Chemical reaction between the gaseous reactant and the solid at the interface
II (b) Diffusion of the product gas through the product
I (b) Diffusion of the gaseous product through the boundary layer

 Chemical control: if the diffusion resistance is negligibly small

 Transport control: if the contribution of the chemical reaction to the
overall resistance is negligible
 Mixed control: two or more of the resistance offers to the progress of
the reaction
Step I (a) Mass transfer through boundary layer

𝑛𝐼 = mass transfer coefficient x surface area x concentration gradient

Where KM(I) is the mass transfer coefficient for the transfer of the gaseous species
between the gas phase and the surface of the pallets, ro is the radius of the pellet,
PIG is the partial pressure of the reactant gas I in the bulk, PIS is the partial pressure
of the reactant gas I at the surface of the pellet, R is the gas constant and T is the
temperature in K.
𝒅𝒓
Eliminating n between 𝒏 = 𝟒𝝅𝒓𝟐 𝝆 and above equation, and integrating resulting equation between the limits ro and r, and
𝒅𝒕
0 and t
RT Where r* is the radius of the reacting front given by r/ro

If tc is the time required for the complete reduction of the pellet and if t is the time
taken for the radius of the reaction front to the changed to r
Step II (a) Diffusion through product layer

Where DI(eff) is the diffusivity of the reactant gas in the product layer
and PIR the pressure of the reactant gas at the reaction front

𝒅𝒓
Eliminating nI between 𝒏 = 𝟒𝝅𝒓𝟐 𝝆 𝒅𝒕 and above equation, and integrating resulting equation between the limits ro and r, and
0 and t

If tc is the time taken for complete reduction, then

This step involves the diffusion of the gaseous species through a porous solid
Step III Chemical reaction a the interface

• The gaseous reactants are get adsorbed at the solid reactant surface and the adsorbed molecules take part in a chemical
reaction to form the product solid and a gas
• The gas gets desorbed from the surface before it is transported out through the product layer
• The reaction rate depends on the concentration of the reactants adsorbed at the surface
The reaction is
Where, Kf is the chemical rate constant of the
forward rate reaction (cm/sec)

If the reaction is reversible, Kb is the chemical

rate constant of the backward reaction

Where Keq is the equilibrium constant

 Kf is normally called the chemical rate constant Kc

𝒅𝒓
Eliminating n between 𝒏 = 𝟒𝝅𝒓𝟐 𝝆 and above equation, and integrating resulting equation between the limits ro and r, and
𝒅𝒕
0 and t , the equation showing the dependence of fractional reduction on time t is obtained as

or

Where K’c is a constant. If tc is the time taken for complete reduction, then
The driving force for the above three steps is the difference in the concentration of the gas in the bulk and that at the reaction
front
𝑷𝑰𝑮 𝑷𝑰𝑺
1. For mass transfer through the boundary layer, the driving force is 𝑹𝑻 − 𝑹𝑻
𝑷𝑰𝑺 𝑷𝑰𝑮
2. For diffusion through the product layer, the driving force is −
𝑹𝑻 𝑹𝑻
𝑷𝑰𝑹 𝑷𝑰𝑰𝑹
3. For the chemical reaction, the driving force (for forward and backward reaction) is −
𝑹𝑻 𝑹𝑻𝑲𝒆𝒒
𝑷𝑰𝑮 𝑷𝑰𝑰𝑹
The overall driving force is −
𝑹𝑻 𝑹𝑻𝑲𝒆𝒒

The rate of reduction of the pellet can be expresses in term of an overall concentration difference or driving force and
an overall resistance corresponding to the above three steps

In practice, the concentration of the reactant and product gases are difficult to determine at the intermediate stages. The
partial pressure of the gas in the bulk PIG can be eliminated, whereas the concentration of the product gas PIIR at the
interface cannot.