Principles of Extractive

Metallurgy

Vant Hoff Isotherm

Vant Hoff isotherm is a very useful expression
which correlates the free energy change in a
reaction occurring at a given temperature to the
corresponding equilibrium constant.
For the homogeneous reaction, A + B C + D,
the Vant Hoff isotherm is expressed by:
G = R T ln K + R T ln Q
where G is the free energy change for the
reaction with the reactants and the products in
arbitrary states; K is the equilibrium constant and
Q is the arbitrary reaction quotient defined

importance of the Vant Hoff isotherm - gives the

direction of a chemical reaction. If under a given set
of conditions G is positive, then the reaction cannot
take place under these conditions.
It may, however, occur if the conditions (activities)
are suitably altered to make G negative.

Vant Hoff Isotherm

Sign of G depends on the relative values of K and
Q. The latter must be smaller than the former for
the reaction to be spontaneous.This will be so
because G would then be negative
First, activities of the products may be decreased
and/or those of the reactants increased, in order
that the value of Q may be made smaller than that
of K.
Second, temperature may be changed in such a
manner as to increase K sufficiently so that the
condition Q < K is satisfied and G becomes
negative

Vant Hoff Isotherm

The result of deviation from unit activity is illustrated
by the reduction of magnesia (MgO) with silicon.
According to data provided, G0 for
2 MgO (s) + Si (s) = 2 Mg (G) + SiO2 (s)
at 1200 C is about +65 kcal.
This implies that there is a very little chance of using
silicon as a reducing agent to produce magnesium
from magnesia.
However, the actual free energy change (G)
accompanying this reaction is provided by

Vant Hoff Isotherm

If PMg (G) and aSiO2 (s) can be brought down
sufficiently, G can be made negative even though
G0 is positive.
The Pidgeon process for the commercial production
of magnesium lowers PMg by operating the process at
a pressure of about 104 atm
and by having CaO present in order to reduce the
activity of the silica in a slag as the orthosilicate 2
CaO SiO2
A basic slag would give aSiO2 as less than 0.001.
The high affinity of CaO for SiO2 brings down the
possibility of loss of MgO as magnesium silicate

Vant Hoff isochore allows one to calculate the effect

of temperature on the equilibrium constant.
G0 = H0 T S0 and G0 = R T ln K
or
R T ln K = H0 + T S0

Free EnergyTemperature
Diagrams
In all metallurgical processing, heterogeneous
reactions and the approach to equilibrium
between two or more phases are of great
importance
Plots of G0 versus T are slightly curved.
G0 = Constant + a T log T + b T2 + C T1 + e T
and
G0 = A + B T log T + C T
where a, b, c, e and A, B, C are constants

Ellingham Diagrams
A particular case of the free energy change
accompanying a chemical reaction is the
standard free energy of formation,
which is the free energy change accompanying
the formation of one mole of a compound from
the constituent elements, all being in their
standard states
the free energies of formation change with
temperature and, without any serious loss of
accuracy, this temperature dependence can be
taken to be linear.

Ellingham Diagrams
M (s) + O2 (g) MO2 (s)
G0 = H0 T S0 is of the form y = m x + c (with
m = S0 = (S S) where S is the total
entropy of the products and S is the total entropy
of the reactants, and c = H0).
The intercept of the graph on the y axis is H
where H is the standard enthalpy at 0 K.
At 0 K, G = H.
The slope of the graph is S0.

Ellingham Diagrams
When the entropy is increasing (S is positive), the
slope of the graph is negative (m = (+ S) = S).
In Figure 3.4. Line 2 corresponds to an endothermic
reaction with the entropy increasing.
Line 4 corresponds to an exothermic reaction with
entropy increasing.
When the entropy is decreasing (S is negative) the
slope will be positive (m = (S) = +S).
Figure 3.4 Line 1 corresponds to an endothermic
reaction with entropy decreasing (G is always
positive), and line 3 shows an exothermic reaction
with entropy decreasing

Ellingham Diagrams
Line 1 represents a typical case of phase
transformation in reactant
In Figure 3.5, line 3 represents a typical case of
phase transformation in the product.
Line 2 illustrates the special case where there is
almost no entropy change associated with the
oxidation reaction and where no phase
transformation of the metal or its oxide occurs in
the range of temperatures considered.
Line 4 in the diagram pertains to another special
situation which arises when oxidation causes an
increase in entropy

Ellingham Diagrams
Typical examples of line 1 behavior are
provided by magnesium, calcium, and zinc.
The classic example of line 2 behavior is
exhibited by carbon dioxide. However, this type of
behavior is not exhibited by any metal.
The oxides of metals like lead and cadmium are
examples of line 3 behavior.
Line 4 behavior is exhibited by carbon
monoxide, and volatile suboxides of several
refractory metals.

Ellingham Diagrams
Ellingham diagrams have been constructed for
sulfides, halides, carbides, nitrides, silicides,
phosphates, sulfates and carbonates
They readily provide information regarding the
temperature range of stability of the compounds
of interest under standard conditions.
A very useful feature of an Ellingham diagram is
that it can provide information pertaining to the
relative stabilities of compounds of the same type
formed by different metals

Ellingham Diagrams
The Ellingham diagram, given in Figure 4.9, is the
logical starting point for considering metal preparation
by oxide reduction.
The less-stable metal oxides appear in the top region of
the diagram; oxides of moderate stability occupy the
middle region; and very stable ones occupy the bottom
region of the diagram
Even among the least stable oxides, only those of the
more noble metals (e.g., silver, platinum, palladium)
can be converted to the metals merely by simple
thermal decomposition; all other oxides can be
converted to metals only by the use of reducing agents.

Ellingham Diagrams
It is possible to divide all the oxides into two
groups, depending on whether the associated
Ellingham line lies above the carbon line or below
it.
For an oxide belonging to the former group, the
carbon line is in the stability field of the metal
and so carbon can, in principle, reduce the oxide
to the metal
Oxides such as cupric oxide, nickel oxide and
many others lie above the carbon line at all
temperatures

Ellingham Diagrams
When the Ellingham line associated with an oxide
intersects the carbon line, the temperature of
intersection represents the minimum temperature
at which the oxide may be reduced by carbon.
Ferrous oxide, for example, can be reduced by
carbon only above 675 C.
It can similarly be seen that several important
nonferrous metal oxides can be reduced by
carbon at temperatures around 1000 C.
These include oxides of tin, lead, copper, nickel,
and zinc.

Predominance Diagrams
2 C + O2 = 2 CO
In the reaction shown above, the volume of the
reaction products (2 mol CO) is seen to be much
greater than that of the reactants (2 mol of solid
carbon plus 1 mol of oxygen).
effect of pressure on the free energy of formation
of an oxide associated with an increase in the
number of gas molecules
which is representative of the type of reaction in
the present
illustration is shown in Figure 4.2 (A).

Predominance Diagrams
2 M + O2 = 2 MO
it is observed that free energy of the reaction
would be lowered, or in other words made
more negative by an increase in O2 pressure, as
shown in Figure 4.2 (B).
Superimposing these two plots as in Figure 4.2 (C)
in order to examine the reduction reaction
2 MO + C = 2 M + 2 CO

Predominance Diagrams
it is observed that at higher pressure the reaction
temperature (the temperature at which free
energy of the reaction becomes zero) is higher.
The two intersecting points on Figure 4.2 (C) can
be regarded as two points on a plot of reaction
temperature against pressure.
Such a presentation or plot appears in Figure 4.2
(D) and is called Predominance diagram

Predominance Diagrams
it relates to the chemical species that will be
dominant, when equilibrium is attained, if the
temperature and pressure in the reactor are kept
fixed.
if the point representing the temperature and
pressure is above the curve, MO and C will be
dominant at equilibrium; below the curve M and
CO will dominate.

Predominance Diagrams
Figure 4.3 provides a fine example of this, and
illustrates a metalsulfuroxygen (MSO) system.
This diagram shows the ranges of gas
compositions (partial pressures of sulfur dioxide
and oxygen) over which each phase (M, MS, MO,
MSO4) exists singly, or in equilibrium with another
phase or phases.
Application of the phase rule to the threecomponent (ternary) system MSO shows that at
a fixed temperature and a given total pressure of
the gas phase, a maximum of three condensed
phases can co-exist.

Predominance Diagrams
For example, if the conditions of roasting
correspond to any point in the region marked MO
in the figure,the end product will be an oxide;
if the conditions correspond to a point on the line
separating the MO and the MSO4 regions, then a
mixture of the sulfate and the oxide will be
obtained by roasting.
The metal will be the end product of roasting if at
the temperature T the values of PSO2 and PO2 are
maintained within the M region.

Pourbaix Diagrams
concerned with the thermodynamics of aqueous
systems
These diagrams are as useful to
hydrometallurgists as are, for example, Ellingham
diagrams to pyrometallurgists.
Thermodynamic considerations are important in
leaching in that they provide basic guidance in
choosing the combination of reagents and
their concentrations so as to obtain favorable free
energy changes associated with any proposed
reaction

Pourbaix Diagrams
two independent variables, the pH and the
potential, are of major concern in the construction
of Pourbaix diagrams
Thermodynamic data applied towards the
prediction of general conditions likely to favor the
dissolution of a mineral in a given aqueous
medium
The creation of boundaries in a potentialpH
diagram results in the formation of areas,in each
of which a particular species is
thermodynamically stable

Pourbaix Diagrams
The first example relates dissolution of zinc metal in
Figure 5.2 (A)
The dissolution of a metal is electrochemical in
nature and, as the potential for the dissolution of zinc
is more negative than both of the above reactions,
each of them can serve as a cathodic process to
support the anodic dissolution of zinc.
It may be seen from Figure 5.2 (A) that solubilization
is favorably disposed below a pH of about 6.9 with
the production of Zn2+ ions (cations) and
beyond a pH of about 13.4 with the formation ZnO 22
ions (anions

Pourbaix Diagrams
In the case of Figure 5.2 (B) for copper, the
Cu2+ + 2 e Cu
equilibrium has a more positive potential than the
hydrogen evolution reaction, but it is more
negative than that of the oxygen reduction
reaction.
copper is not solubilized by means of hydrogen
evolution as the cathodic process
referred to as a noble metal and its solubilization
is only accomplished by the reduction of oxygen
or some other oxidizing agent.

Pourbaix Diagrams
gold, it is known to be a more noble metal than
copper, and the potential of the
Au3+ + 3 e Au
equilibrium is more positive even that of the oxygen
reduction reaction (Figure 5.2 C).
metal does not respond to leaching by normally
known strong oxidizing acids.
the leaching of gold ores is not at all easy