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Kinetics of Metallurgical Processes

General Considerations
Metallurgists and Chemical engineers primarily deal with
• Extraction and refining of metals
• Developments of alloys
• Development of new products and modification of an existing one

 While metallurgical processes are at high temperature, the systems dealt by


chemical engineers at a fairly moderate temperature
 The systems encountered by both metallurgical and chemical engineers may
involve single or multiple chemical reactions

A chemical reaction is associated with two important aspects:


 Thermodynamics
 Kinetics
Thermodynamics Versus Kinetics
Reactant X transforming to Y using certain reaction path

Thermodynamics predicts
 feasibility of the reaction under a given set of condition
 composition of the co-existing phases at certain temperature
and pressure
The above are assessed assuming equilibrium
What thermodynamics can not tell about the reacting system:
 How fast
 How far
 Which reaction path
 What mechanism

Chemical kinetics fills up the shortcomings of thermodynamics


Characteristic feature every reacting system
Thermodynamic driving force
 Energy issue

How to visualize:
GI, Gf : Gibb’s free energy of reactant and product
∆G = GI-Gf Thermodynamic driving force

GA = Energy barrier for the reaction


Related to kinetics

In general ;
Rate α Kinetic factor X thermodynamic factor

Favourable thermodynamic factor does not


ensure occurrence of a reaction
Thermodynamically feasible but kinetically
unfavourable
 Diamond to Graphite
 H2 and O2 reaction
 Transformation of metastable structure

Point to remember
Thermodynamics has nothing to do with time
 Thermodynamics may be called as Thermostatics

Domain of Kinetics:
 Occurrence of chemical reaction
 Rate
 Mechanism
Classification of chemical reaction
Consider a generalised reaction:
A (S) + B (g) C(s) + D(g)
The steps involved are:
(1) Transport of gaseous reactant from bulk gas phase to the particle surface
through a boundary gas film
(2) Molecular diffusion of the gaseous reactant through product layer to the reaction
interface
(3) Adsorption of gaseous reactant on the solid surface
(4) Reaction at the interface
(5) Desorption of the gaseous product from the interface
(6) Ionic transport within the solid phase and phase transformation, if any
(7) Molecular diffusion of gaseous product through the product layer to the solid
particle surface
(8) Transport of the gaseous product through boundary gas film
(9) Transport of gaseous product to the balk gas phase

Steps (3), (4) and (5) involve some chemical activity


Rest steps involve transport of species (reactant or product)

Slowest of the above steps determines the overall speed of reaction, the Rate
Controlling Step
Classification of Reactions:
Most widely used classification is based on the number and type of phases
involved

Homogeneous Reaction: If reaction takes place in one phase alone


Most gas phase and liquid phase reactions

Heterogeneous Reaction: If involves at least two phases


Burning of coal, Gas – liquid adsorption

Definition of reaction rate:


If rate of change of moles of i is dNi/dt, then
For reacting fluid
Rate (ri) = 1/V (dNi/dt) Moles of i /(Vol. of fluid) (time) (Unit vol. basis)
For solid- fluid system
= 1/W (dNi/dt) Moles of i /(mass of solid) (time) (Unit mass basis)
For two fluid system
= 1/S (dNi/dt) Moles of i /(Interfacial area) (time) (Unit surface area)
For solid – gas system
= 1/Vs (dNi/dt) Moles of I/ (Vol. of solid) (time) (Unit vol. of solid)
Variable affecting rate of reaction

For homogeneous system


 Temperature
 Pressure
 Composition

For Heterogeneous system


 variables for homogeneous system
 Interfacial reactions
 Mass transfer between phases
 Heat transfer between phases
Kinetics of Homogeneous Reaction

Points to note:
 Reaction is contained within a single phase
 Extensively used rate expression
Rate (rA)= 1/V (dNA /dt)
 Rate depends upon the state of the system
Rate (rA) = f (temperature, pressure, composition)
 Rate does not depend upon
Shape of the container
Surface properties
Diffusional properties etc.
 Pressure depends upon temperature and composition, thus
Rate (rA) = f (temperature, pressure, composition)

In Homogeneous system, Temperature and composition are of interest in


determining the rate
Dependence of rate on composition/concentration
Nomenclatures in Chemical reactions

Single reaction:
• Single stoichiometric equation and single rate expression

Multiple reaction
• More than one stoichiometric equation and multiple rate expressions
Series: A R S
R
Parallel : A S
Complicated:
A+ B = R
R+ B = S
Elementary Reaction

• Rate equation corresponds to stoichiometric equation

A+B D
- rA = k. CA . CB k = rate constant
Non- Elementary Reaction
No correspondence between the stoichiometry and the rate equation
H2 + Br2 = 2 HBr

k1 [H2] [Br2]½
RateHBr = ----------------------------
k2 + [HBr]/[Br2]

An overall reaction can be viewed as a combination of multiple


elementary reactions

Points to note:
 Rate depends upon path
 One or more simple steps may be involved
 Each simple step (elementary) step ensures minimum rearrangement of
atoms
 Rate of slowest elementary step determines the overall rate of reaction
 Order of the rate controlling reaction is the order of the overall reaction