Extractive Metallurgy

THERMODYNAMIC PRINCIPLES

THERMODYNAMICS

There are three types of systems: (a) closed systems

(or nonflow systems); (b) open systems (or flow
systems), and (c) isolated systems.
A closed system is a system of fixed mass. No mass
transfer occurs across the system boundary.
However, there can be energy transfer into or out of
the system.
A certain quantity of fluid in a cylindrical container,
bound by a piston, constitutes a closed system

THERMODYAMICS

An open system is one in which matter (or mass) can

cross the boundary of the system. In addition, there
can also be energy transfer.
In an isolated system is there is no interaction
between the system and the surroundings.
It is of fixed mass and energy, and there is no mass
or energy transfer across the system boundary

THERMODYAMICS

The state (or behaviour) of a system is described by

variables or properties which may be classified as:
(a) extensive properties such as mass, volume,
kinetic energy; and
(b) intensive properties which are independent of
system size, e.g., pressure, temperature,
concentration.

THERMODYAMICS

An extensive property can be treated like an

intensive property by specifying that it refers to a
unit amount of the substance concerned.
Thus, mass and volume are extensive properties, but
density, which is mass per unit volume, and specific
volume, which is volume per unit mass, are intensive
properties

THERMODYAMICS

There are two types of processes: reversible and

irreversible
In a reversible path, when a given process has been carried
out and then reversed, both the system and its
surroundings come back exactly to their original states and
no net change occurs in any part of the system or the
surroundings.
On the other hand, a process which involves the
spontaneous transition of a system from a non equilibrium
state to an equilibrium state is called an irreversible
process.
An irreversible process is also called a spontaneous or a
natural process

ZEROETH LAW

The zeroeth law of thermodynamics states that when

a substance A is in thermal equilibrium with a
substance B, and also separately with a substance C,
then B and C will be in thermal equilibrium with each
other.
According to this law, A, B and C are said to be
equally hot or at the same temperature.

FIRST LAW

(i) energy can neither be created nor destroyed

though it may be converted from one form to
another;
A closed system undergoing a change of state or a
process is considered.
Although mass transfer is prohibited across the
boundaries of a closed system, energy transfer is
permitted.
This energy transfer can occur as work and heat
transfer, both of these being only different forms of
energy.

FIRST LAW

U = q w
Here, q is considered to be the heat absorbed by the
system from the surroundings and w, the work done
by the system on the surroundings.
The terms q and w are written with lower-case
letters to indicate that they are not functions of the
state of system.
The heat capacity, C, of a system is defined as the
heat introduced or withdrawn to raise or lower the
temperature of the system by one degree celsius

FIRST LAW

heat capacity at constant volume is the rate of

change of internal energy with temperature,
while heat capacity at constant pressure is the rate
of change of enthalpy with temperature
Cp= a+ b T+ C T-2
where a, b, and c are constants (for a given
substance) and T is the temperature in degrees
Kelvin.

FIRST LAW
Metallurgical processes are mostly carried out at
constant pressure and, therefore, enthalpy assumes
the role of a very important thermodynamic
parameter in metallurgical thermochemistry.
The heat absorbed in a process at constant pressure
is equal to H, the increase in the enthalpy of the
system
This quantity is called the heat of reaction, H, and
can be expressed as follows
H = H (products) - H (reactants)

FIRST LAW

The heat of formation of a compound is the change in

enthalpy that results when one mole of the compound is
formed from its constituent elements.
The heat of combustion of a substance is the enthalpy
change that occurs when one mole of the substance (an
element or a compound) is completely burnt in oxygen.
The heat of transformation is defined as the change in
enthalpy that results when one mole of a substance
undergoes a specific change of state such as melting,
evaporation, or allotropic modification.
The heat of solution is the enthalpy change that occurs
when one mole of the solute is added to form a solution of
a particular concentration.

FIRST LAW
Hesss law states that the overall change in enthalpy
in a reaction is the same whether the reaction takes
place in one step or through a number of
intermediate steps
C + 0.5 O2 = CO (H0298 = 110530 J)
CO + 0.5 O2 = CO2 (H0 298 = 282980 J)
Adding,
C + O2 = CO2 (H0 298 = 110530 J 282980 J =
393510J)

SECOND LAW

the second law may be stated as: in every process

occurring in an isolated system, the entropy of the
system either increases or remains constant.
It increases in an irreversible process and remains
constant when the process is reversible
Entropy can be described by considering a closed
system undergoing a reversible process.
The entropy change, dS, of the system is defined by
the relationship
dS Q/T

SECOND LAW

The equality applies when heat is transferred

reversibly and the inequality refers to irreversible or
natural or spontaneous transfer of heat
It has been shown that the entropy of an isolated
system increases in every natural (i.e., irreversible)
process
The entropy of a nonisolated system may either
increase or decrease, depending on whether heat is
added to it or removed from it and whether
irreversible processes occur within it

FREE ENERGY

Greater practical convenience and utility

Helmholtz free energy, represented by the symbol A,
is defined as: A = U T S
In this expression U is the internal energy, T is the
absolute temperature and S is the entropy.
Gibbs free energy, represented by the symbol G (the
symbol F is also sometimes used in place of symbol
G), is defined as:
G=HTS

FREE ENERGY

dG = dU T dS S dT + V dP + P dV
dU = T dS P dV
dG = V dP S dT
These relationships interrelate the parameters
pressure, volume and temperature with the Gibbs
free energy of a system

FREE ENERGY

The free energy change in a chemical reaction is

expressed in the same way as the enthalpy of the
reaction is expressed
For example, the free energy change in the reaction
aA+bB=cC+dD
is
G = c GC + d GD a GA b GB
or
G = G (products) - G (reactants)

FREE ENERGY

For a finite process occurring at constant temperature T

and pressure P, the free energy change can be expressed
as
G = H T S
The above equation is especially valuable in highlighting
the importance of change in free energy as an explicit
criterion for the spontaneity of a chemical reaction.
At constant temperature and pressure, dG = dU T dS +
P dV, and so for any process,
dGT,P 0
where the less than sign refers to a spontaneous
process and the equal to sign to an equilibrium process

FREE ENERGY

Since dGT,P is either less than or equal to zero,

depending on whether the system undergoes a
spontaneous change or is in an equilibrium state,
it follows that for a system in equilibrium, at a given
temperature and pressure, the free energy must be a
minimum
All the spontaneous processes occurring at constant
temperature and pressure are accompanied by a
decrease in the free energy
This result is of fundamental importance for it gives a
simple and convenient criterion for assessing whether
a given process is possible or not

THIRD LAW

the entropy, S, of any perfectly ordered crystalline

substance at absolute zero should be zero.
This is the statement of the third law of
thermodynamics. The third law, therefore, provides a
means of calculating the absolute value of the
entropy of a substance at any temperature.
The statement of the third law is confined to pure
crystalline solids simply because it has been
observed that entropies of solutions and supercooled
liquids do not approach a value of zero on being
cooled.

Figure 3.1 (A) Plots for the

change in enthalpy and free
energy of a reaction
as a function of temperature;

CHEMICAL EQUILIBRIUM

A general reaction of the type in which reactants R1

and R2 from products P1 and P2 at a given
temperature is considered. This is expressed as a
forward reaction by:
R1 + R2 P1 + P2
Again, P1 and P2 react to regenerate R1 and R2. This
is expressed as a reverse reaction by:
P1 + P2 R1 + R2
These two oppositely directed reactions are
represented by a single equation as:
R1 + R2 P1 + P2

CHEMICAL EQUILIBRIUM

Every reversible reaction, depending on its nature, will

after some time reach a stage when the reactants and
the products coexist in a state of balance, and their
amounts will remain unaltered for unlimited time.
Such a state of a chemical reaction is called chemical
equilibrium, and the point of such an equilibrium varies
only with temperature.
reactions which are ordinarily found to proceed to
completion in one direction are said to be irreversible
reactions. Ex- The decomposition of potassium chlorate
2 KClO3 2 KCl + 3 O2

CHEMICAL EQUILIBRIUM

There are two different approaches, namely, kinetic

and thermodynamic, which are useful for describing
chemical changes and chemical equilibria
According to the kinetic approach, the equilibrium
state results from a dynamic balance between
opposing reactions.
The thermodynamic approach defines the equilibrium
state as one of maximum stability, i.e., one of
minimum free energy
Both kinetic and thermodynamic approaches lead to
identical descriptions of the chemical compositions
corresponding to the equilibrium state

CHEMICAL EQUILIBRIUM

The kinetic approach is useful for gaining an

understanding of chemical reactions and of the
mechanisms of their approach to equilibrium.
The thermodynamic approach is useful for assessing
the effects of factors such as temperature, pressure,
volume, and composition on chemical equilibrium
Law of mass action - at constant temperature, the
rate of a chemical reaction varies directly as the
molar concentration of the reacting substances

CHEMICAL EQUILIBRIUM
A+BC+D
[A], [B], [C], and [D] denote the molar concentrations
of the species A, B, C, and D respectively at
equilibrium
Forward velocity of reaction can be expressed as kf
[A] [B], where kf is known as the forward velocity
constant and represents the rate of the reaction
when both [A] and [B] equal unity
Rate of formation of A and B would be expressed as
kr [C] [D], where kr is the reverse velocity
constant

CHEMICAL EQUILIBRIUM

At the equilibrium point, the forward velocity of the

reaction would equal its reverse velocity:
kf [A] [B] = kr [C] [D]

CHEMICAL EQUILIBRIUM

2 AB (g) A2 (g) + B2 (g)

CHEMICAL EQUILIBRIUM-CRITERIA

Permanency: at a given temperature, when the system has

attained a state of equilibrium, it does not change further with
time. In other words, the composition of the equilibrium
mixture remains unchanged forever.
Approachability from both sides: at a given temperature a
reaction typically representable by A + B C + D attains
exactly the same state of equilibrium irrespective of whether
it is started with the reactants, A and B or the products, C and
D.
Incompleteness of the reaction: this is the chief criterion of
chemical equilibria. A reversible reaction is never complete in
any direction provided none of the products is allowed to
escape from the system

SOLUTIONS

Molten phases play a prominent role in extractive

metallurgy
In a smelting process, for instance, the valuable
components of a resource material enrich one
molten phase,
whereas the gangue and other impurities are
discarded in another, called the slag phase.
There are also gases in metals which provide
examples of solutions consisting of solids or liquids
as solvents and gases as solutes

RAOULTS LAW
Raoults law is expressed as
PA = PAo XA
PB = PBo XB
where XA is the mole fraction of the component A
and XB is the mole fraction of the component B
figure shows plots of the vapour pressures of the
components A and B and also of the total vapour
pressure of both A and B as a function of
composition

HENRYS LAW

Henrys law can be stated as follows: the vapor pressure

of a component over a solution is proportional to its mole
fraction. For the component A, this relation is given by
PA XA
P A = KA XA
where KA is a constant characteristic of the component
and the solution at a given temperature.
Henrys law is obeyed by either of the components, and
not by both the components at the same time.
Henrys law is obeyed by the solute over only a limited
range of concentrations, usually in the dilute solution
range

SEIVERTS LAW

dissolution of gases in metals is an important area

that warrants special attention in metallurgy
Sieverts law can stated as: the solubility of a
diatomic gas in a liquid metal is proportional to the
square root of its partial pressure in the gas in
equilibrium with the metal.
nitrogen for instance, dissociates into atoms when it
dissolves in a metal.
XN = (PN2 )0.5 x constant
Sieverts law behaviour of nitrogen in niobium is
illustrated in Figure 3.8.

SEIVERTS LAW

Molten metals produced in the presence of air typically

contain significant quantities of dissolved nitrogen,
oxygen, and hydrogen (from the water vapor present in
air).
It is usually necessary to remove these gases prior to
solidification, because their solubilities in the solid metal
are much smaller than those in the liquid metal.
Consequently, on solidifying a metal with a high
concentration of dissolved gases, voids are formed in the
solid from the evolved gas bubbles;
these could degrade the mechanical properties of a
casting and additional processing would be required to
eliminate such voids.

ACTIVITY AND ACTIVITY COEFFICIENT

more accurate method of expressing concentrations of

components in a solution is by specifying their activities
activity, ai, of a component, i, in a solution is defined as
the ratio of the partial pressure, Pi, of the component in
solution to the partial pressure, 0 Pio , of the pure
component at the same temperature.

ACTIVITY AND ACTIVITY COEFFICIENT

It can be immediately seen from the above relationship
that when a component obeys Raoults law, its activity is
equal to its mole fraction
ai = X i
Similarly, when Henrys law is obeyed,
a i = ki X i
where ki is a constant for the solute i at a given temperature
activity coefficient, i, of the component, i, in a solution is
defined as the ratio of its activity, ai, to its mole fraction,
Xi,

FREE ENERGY FORMATION OF A SOLUTION

process of formation of a solution between two

substances, A and B, can be represented as
A + B = AB
and
GM = GAB GA GB
Here, GM is the free energy change for the above
process and is called the free energy of mixing.
GAB is the free energy of the solution, while GA and GB
are the free energies of the pure components A and
B respectively.
A solution forms if GAB < (GA + GB) i.e., if GM is
negative

FREE ENERGY FORMATION OF A SOLUTION

free energy of mixing (GM) is related to the

corresponding enthalpies (HM) and entropies (SM) by the
equation
GM = HM T SM
mole fractions of A and B given by XA and XB respectively,
the free energy of one mole of the solution G A-B is given by
GA-B = XA GA + XB GB
partial molar free energy of the component A in the
solution is defined as the increase in the free energy of
the solution A-B when one mole of A is added to a large
quantity of the solution at a given temperature and
pressure

FREE ENERGY FORMATION OF A SOLUTION

the partial molar free energy, GA, of the component

A, is expressed as

ere G is the free energy of the solution, nA is the number of moles of A,

of B and the subscripts shown outside the bracket imply that T, P and nB
maintained constant as nA is varied

r the binary solution A-B, the integral molar free energy

mixing is then

GIBBS DUHEM EQUATION

GibbsDuhem equation is one of the most

extensively used relations in thermodynamics

IDEAL SOLUTION

In an ideal solution the components obey Raoults

law. The activity equals the mole fraction:
ai = Xi
There is thus no volume change associated with the
formation of an ideal solution.
The enthalpy of formation of an ideal solution is also
zero

NON IDEAL SOLUTION

Any solution in which the activity of a component is

not equal to its mole fraction is called non-ideal.
The extent of the nonideality of a solution, i.e., the
extent of its deviation from the ideal behaviour, is
easily quantified in terms of the value of the activity
coefficient
when < 1, the component is said to exhibit a
negative deviation from Raoults law
When the activity coefficient exceeds unity, the
component is said to exhibit a positive deviation
from Raoults law

REGULAR SOLUTION

regular solution which is characterized by a nonzero

enthalpy of mixing but an ideal entropy of mixing

e integral molar excess free energy of mixing as well as the enthalpy of

mixing are independent of temperature for a regular solution.

PHASE RULE

phase rule deals with the behavior of heterogeneous

systems at equilibria
includes three special terms.
These are: (i) number of phases in the system (P);
(ii) the number of components for the system (C);
and (iii) the number of degrees of freedom available
to the system (F)
F = C P + 2 or P + F = C + 2
number of components is defined as the minimum
number of independently variable chemical
constituents

PHASE RULE

(i) freezing water has three phases,ice, water and

vapour in equilibrium;
(ii) a mixture of two or more gases is homogeneous
and constitutes one phase only;
(iii) two immiscible liquids in contact form two
different phases; and
(iv) a heterogeneous mixture of solid substances
consists of as many phases as there are substances
present.

PHASE RULE

diagram consists of two curves, AO and BO.

The curve AO shows the effect of the addition of lead on
the melting point of pure silver and may be designated
as the melting point or the freezing point curve of silver.
All along the curve AO there are two phases, solid silver
and liquid, in equilibrium; therefore
F = C P + 1 = 2 2 + 1 = 1, indicating that the
system is univariant
curves AO and BO meet at O which, represents the
conditions under which solid silver, solid lead and the
liquid solution coexist. The degree of freedom here is
zero; that is, the system is invariant.