JIMMA INSTITUTE OF TECHNOLOGY

Faculty of Materials Science and Engineering

Thermodynamics of materials (II)
By: Sefu Taye

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 Objective/Expected Learning Outcomes
Upon completion of the course, students will be able to:
✓ Make simple inference from the solutions to simple
thermodynamic problems.
✓ Solve simple and complex problems related to different
thermodynamic principle.
✓ Analyze the equilibrium conditions between solid-liquid,
liquid-gas and solid-gas phases in one-component systems,
and multi-component system.
✓ Apply Raoult's and Henry's laws, and regular solution rules
to open systems. Derives simple binary phase diagrams using
given thermodynamic data in systems showing Raoultian
behavior.
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✓ Describe the formation of a solution from its pure
components.
✓ Analyze the relationship between Gibbs free energy,
thermodynamic activity and phase diagrams.
✓ Draws equations expressing change in Gibbs free energy
of mixing of liquid and solid solutions as a function of
composition, and plot diagram showing these variations
for a given standard state

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 Chapter – 1
Thermodynamics
of
materials
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 Unit one contents
• Introduction to thermodynamics
• Thermodynamics of a reaction:-
✓Electrochemical cells,
✓Solid electrolytes
✓Pourbaix diagrams
• Thermodynamics of Surfaces :-
✓Adsorption isotherms
✓Surface energy effect on Pressure & Phase
transformation temperature
• Thermodynamics of Defects in solids

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 Introduction
• Thermodynamics Thermal +
Dynamics(scien
(Heat) ce of motion)

Is the science Heat

of the Energy
relationship Temperature
between:
Work

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 Laws of thermodynamics
Zeroth laws of thermodynamics:-if two
thermodynamic systems are each in thermal
equilibrium with the third thermodynamic system,
they are also in thermal equilibrium with each other.
A
= =
B = C
First law of thermodynamics:- The change in internal
energy of the system is equal to heat added to the
system minus the work done by the system.

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 Heat Surrounding
System

Work

-W - work done by the surrounding

ΔU = Q - W
+W – work done by the system

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 Questions
1. What is the difference between:
a. ΔU = Q – W
b. ΔU = Q + W
2. What is the internal energy of system, if the
surrounding lose 100J of heat and if the system
does 250J of work on the surrounding?

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 Second law of thermodynamics
✓ Heat will never be flow spontaneously from colder
object to hotter object.
✓ The total disorder will never be seen to decrease.
Third law of thermodynamics:- The entropy of a perfect
crystal is zero at absolute zero temperature.

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 Thermodynamics of a reaction
✓ Thermodynamics determines whether the reaction
between two reactant has enough energy to produce
expected product.
✓ It can lead to predicting how chemical reaction will
proceed or how much energy is required or released
during the reactions.
✓ Electrochemical reactions, especially galvanic cells
are governed by the properties of thermodynamics.

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✓ Electrochemical cell/reaction is the one where either
a chemical reaction produces an electric current, or
where an electric current causes a chemical reaction
to take place.
✓ All electrochemical processes involve redox
reactions.
✓ A redox reaction is one where there is always a
change in the oxidation numbers of the elements
that are involved in the reaction.
✓ It is possible to balance redox equations using the
half-reactions that take place within the overall
reaction.

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Redox reaction = Reduction rxn + Oxidation rxn
✓ Reduction reaction:- is the gain of electron or a
decrease in oxidation number by a molecule, atom,
or ion.
▪ Carried out in cathode electrode.
Examples:- Zn+2 (aq) + 2e− Zn (S) Half-cell
Ag+ (aq) + e− Ag (s) reaction

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✓ Oxidation reaction :- is the loss of electron or an
increase in oxidation number by molecule, atom, or
ion.
▪ Carried out in anode electrode.
Examples:- Na(s) Na+1 (aq) + e- Half-cell
Cu(s) Cu+2 (aq) + 2e- reaction

The overall reaction between two half-cell (reduction +

oxidation) will give as redox reaction.
Example:- Cu(s) Cu+2 (aq) + 2e-
Zn+2 (aq) + 2e− Zn (S)
Overall Rxn :- Cu(s) + Zn+2 (aq) Zn (s) + Cu+2 (aq)

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✓ A substance is oxidised when it undergoes oxidation
reaction and it is also called reducing agent.
✓ A substance is reduced when it undergoes reduction
reaction and it is also called oxidising agent.
Example:- 2Na + Cl2 2NaCl
Na0 Na+ + e-
Here sodium is oxidized and it is reducing agent
Cl0 + e- Cl-
Chlorine is reduced and it is oxidizing agent

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 Question

• Identify the oxidised substance/reducing agent and

reduced substance/ oxidizing agent.

3MnO2 + 4Al 3Mn + 2Al2O3

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 Electrode potential
• It is the tendency of an electrode in half cell to lose or
gain electrons when it is in contact with solution of its
own ion
• Zn (s) Zn+2 (aq) + 2e- Oxidation half rxn
• Cu+2 (aq) + 2e Cu (s) Reduction half rxn
• Magnitude of a cell’s potential measures the
spontaneity of its redox reaction
• Higher cell potentials indicate a greater driving force.

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 Standard Cell Notation (line notation)
Cell notation is a short-hand expression of any reaction
of an electrochemical cell.
In cell notation, a vertical line, |, denotes a phase
boundary and a double line, ||, a salt bridge. The
anode electrode is written to the left, followed by the
anode solution, then the salt bridge, then the cathode
solution, and, finally, the cathode electrode to the
right.
• Anode / anode solution // cathode solution /
Cathode

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 Cell Notation Zn | Zn2+ (1M) || Cu2+ (1M) | Cu

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The electrode is a conductor through which electricity
enters or leaves an object, substance, or region.
✓ The Anode is the negative or reducing electrode that
releases electrons to the external circuit and oxidizes
during electrochemical reaction.
✓ The Cathode is the positive or oxidizing electrode
that acquires electrons from the external circuit and
is reduced during the electrochemical reaction

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 Standard Hydrogen Electrode
It is a reference electrode against which the electrode
potentials of all half-cell reaction are measured.
✓ it is impossible to determine experimentally the
potential of a single electrode.
✓ The value of the standard electrode potential is zero,
which forms the basis one needs to calculate cell
potentials using different electrodes or different
concentrations.

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✓ Metal coated with Pt immersed in a 1.0 M H+ solution.
H2 gas is bubbled at 1 atm over the electrode
✓ Assigned a potential of 0.000 V

2 H+(aq, 1 M) + 2e- <----> H2(g, 1 atm) E° = 0.000V

H2(g, 1 atm <----> 2 H+(aq, 1 M) + 2e- E° = 0.000V

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 Electromotive force (emf)
The electric potential produced by either an
electrochemical cell or by changing the magnetic field.
• The two half-cells are also connected externally. In this
arrangement, electrons provided by the oxidation
reaction are forced to travel via an external circuit to
the site of the reduction reaction.
• The fact that the reaction occurs spontaneously once
these half cells are connected indicates that there is a
difference in potential energy.

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• This difference in potential energy is called an
electromotive force (emf) and is measured in terms
of volts.
• It is also called the cell potential, and is designated
Ecell.
• The zinc/copper cell has an emf of about 1.1 volts
under standard conditions.

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 Electromotive Series
Electromotive series are listing of chemical species
(atoms, molecules, and ions) in the order of their
tendency to gain or lose electrons (be reduced or
oxidized, respectively), expressed in volts and
measured with reference to the hydrogen electrode.
✓ When involve metals in contact with their ions –
electromotive series
✓ Zn: Std. oxidation potential = +0.763 V
✓ Therefore, reduction potential = -0.763 V

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✓ Electromotive series is used to Predict the
spontaneity of redox reactions
• Question: Will Cu+2 oxidize Zn to Zn+2 or will Zn+2
oxidize Cu?

✓ Write half reactions and make sure E° is positive.

• Cu+2 + 2 e- Cu E° = 0.34 V
• Zn Zn+2 + 2 e- E° = -0.76 V
• Therefore, Cu+2 will oxidize Zn to Zn+2

For any two metals in an activity series, the more active

metal is the more readily oxidized

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 An electrochemical cell
✓ Device that can generate electrical energy from
the chemical reactions occurring in it, or that use
the electrical energy supplied to it to facilitate
chemical reactions in it.
✓ These devices are capable of converting chemical
energy into electrical energy, or vice versa.
Types of Electrochemical Cells
Electrolytic Cells: is electrochemical device that uses
electrical energy to facilitate a non-spontaneous
redox reaction.
Electrolytic cells convert electrical energy into
chemical potential energy.

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• Voltaic Cells (Galvanic Cells): is An electrochemical
cell that converts the chemical energy of
spontaneous redox reactions into electrical energy.
The important parts of a voltaic cell: The anode is an
electrode where oxidation occurs. The cathode is an
electrode where reduction occurs.
Salt Bridge → a device used to maintain electrical
neutrality in a galvanic cell
This may be filled with agar which contains a neutral
salt or it may be replaced with a porous cup.

Electron Flow → always from anode to cathode

(through the wire)

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 Nernst Equation
The Nernst equation provides the relation
between the cell potential of an electrochemical
cell, the standard cell potential, temperature, and
the reaction quotient.
Even under non-standard conditions, the cell potentials
of electrochemical cells can be determined with the
help of the Nernst equation.

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 Derivation of Nernst Equation
✓ Consider a metal in contact with its own salt-aqueous
solution.
Mn+ + ne– → nM
✓ In the reduction reaction, ‘n’ moles of an electron is
taken up by the ion against a reduction potential of Ered.
The work done in the movement of electron
Wred = nFEred
Where,
• F is Faraday = 96487 coulomb = electrical charge
carried by one mole of electrons

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 Change in the Gibbs free energy is an indication of
spontaneity, and it is also equal to the maximum useful
work (other than volume expansion) done in a process.
✓ Combining work done and Gibbs free energy change:
Wred = nFEred = – ∆G or ∆G = – nFEred
Change in the free energy at standard conditions of 298
K and one molar /one atmospheric pressure conditions
is ∆G°. From the above relation, it can be written that
∆G° = – nFE°red
Where,
• E°red is the reduction potential measured at standard
conditions.
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During the reaction, concentration keeps changing, and
the potential also will decrease with the rate of
reaction
✓ For a reversible equilibrium reaction, Van’t Hoff
isotherm says:
∆G = ∆G° + RT ln K
Where,
✓ K is the equilibrium constant
✓ K = Product/Reactant = [M]n/[M]n+
✓ R is the Gas constant =8 .314J/K mole
✓ T is the temperature on the Kelvin scale

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Substituting for free energy changes in Van’t Hoff
equation,
– nFEred = – nFE°red + RT ln [M]/[Mn+] = – nFE°red +
2.303 RT log [M]n/[Mn+]
Dividing both sides by – nF,
RT
E =E − ln Q
nF
✓ The equation is sometimes streamlined by restricting
discussion to T = 25 °C (298 K) and inserting the values
for the constants, R and F(1 F = 96,485 C/mol ,).
0.0257
E =E − ln Q lnQ = 2.303 logQ
n
0.0592
E =E − log Q
n
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The relationship between the Nernst equation, the
equilibrium constant, and Gibbs energy change are
illustrated below

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 Nernst Equation Application
The Nernst equation can be used to calculate the
following:
✓ Single electrode reduction or oxidation potential at
any conditions
• Standard electrode potentials
• Comparing the relative ability as a reductive or
oxidative agent
• Finding the feasibility of combining such single
electrodes to produce an electric potential
• Emf of an electrochemical cell
• Unknown ionic concentrations
• The pH of solutions and solubility of sparingly soluble
salts can be measured with the help of the Nernst
equation.
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 Questions

1. What is the Cell Potential of the electrochemical cell

in which the cell reaction is: Pb2+ + Cd → Pb + Cd2+?
Given that Eocell = 0.277 volts, temperature = 25oC,
[Cd2+] = 0.02 M, and [Pb2+] = 0.2 M.
2. Calculate E for a Al – Cu cell in which the
temperature is 20.5 °C and the [Cu+2] = 0.25 M and
[Al+3] is 0.75 M.
Reduction potential for Al+3 /Al = -1.66V and for Cu+2
/Cu = 0.34V

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 Pourbaix Diagrams
A Pourbaix diagram is a plot of the equilibrium
potential of electrochemical reactions against pH. It
shows how corrosion mechanisms can be examined as
a function of factors such as pH, temperature and the
concentrations of reacting species.
The diagrams represent the stability of a metal as a
function of potential and pH
✓ A Pourbaix diagram is like a phase diagram having
ion boundaries represented by lines.

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✓ In practice, Pourbaix diagrams are suitable for
studies of corrosion, electrowinning
electroplating, hydrometallurgy, electrolysis,
electrical cells, and water treatment since they
are electrochemical maps indicating the domain
of stability of ions, oxides, and hydroxides.
Thus, Pourbaix diagrams introduce the concept of
the following three states of metals, depending on
the potential in the given aggressive medium and
the determination of its corrosion behavior:
✓ corrosion (active state),

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 ✓ passivity (forming passive layers inhibiting the
corrosion process on the surface of the metal,
including thermodynamically active metals) and
✓ immunity (thermodynamic stability) of the metals

• Vertical line indicates pure

acidic base reaction
• Horizontal line indicates
pure redox reaction
• Inclined(sloped) line
indicates combination of
acidic-base and redox
reaction

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 Characteristics of a Pourbaix Diagram
✓ The horizontal lines represent electron transfer reactions. They
are pH -independent, but potential-dependent.
✓ The vertical lines are potential-independent but pH-dependent
and not accompanied by any electron transfer.
✓ The sloping, straight lines give the redox potentials of a solution
in equilibrium with hydrogen and oxygen, respectively. This
equilibrium indicates electron transfer as well as pH.
✓ The concentration of all metal ions is assumed to be 10- 6 mol per
liter of solution. At lower concentration, corrosion should not
occur.
✓ The diagram is computed for the equilibrium conditions at 25°C.
✓ The upper end of the redox potential axis is the noble end and
the lower end, the active end, meaning that the oxidizing power
increase with increasing potential.
✓ The hydrogen and oxygen lines are indicated in Pourbaix diagrams
by dotted line.
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 Objectives of Pourbaix Diagram

The main objectives of the Pourbaix diagrams are:

✓ To show the directions of the various reactions at
given pH and potential.
✓ To make a basis for estimation of the corrosion
product compositions at various pH and potential
combinations.
✓ To show which environmental pH and potential
changes will reduce or prevent corrosion.

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 Pourbaix Diagram For Water

✓ Each line of a Pourbaix

diagram represents
conditions of thermodynamic
equilibrium for some
reaction.
✓ The Pourbaix diagram for
water is presented in this
figure, above line b, oxygen is
evolved in accord with the
reaction. Below this line,
water is stable. Below line a,
hydrogen is evolved.

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 Above line b, defined by this equation, oxygen is evolved at the
surface of an immersed electrode. Below this line, water is stable.

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 Constructing a Pourbaix Diagram

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 Pourbaix Diagram for a Metal
✓ Below is a brief description on how to construct a
Pourbaix diagram for a metal M-H2O electrochemical
system, in which the lines represent predominant ion
boundaries enclosing areas of stable phases in an
aqueous environment as shown in figure below.
✓ The construction of the diagram consists of
determining the potential E for lines 1 and 3 using the
Nernst equation and the pH for lines 2 and 4 using
known equilibrium constant Ksp

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✓ The range of metal ion concentration can be 10⁻⁶
mol/ l ≤ a( Mᴢ⁺)≤ 1 mol/ l, but a (Mz⁺)= 10⁻⁶ mol/ l is
chosen hereafter in order to simplify the procedure
for constructing the diagram.
✓ Otherwise, several vertical and incline lines would be
generated.If a (Mz⁺)=1 mol/ l, the electrochemical
corrosion process is unrealistic

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 Schematic Pourbaix diagram for a metal M showing theoretical domains
of corrosion, immunity, and passivation of aluminum at 25 ᵒC. The
hydrogen and oxygen linear trends and the stable water region are
included as references
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The procedure is as follows:
1. Horizontal line 1 with [M]= 1mol/l
(a)

(b)

This reaction involves electron transfer only. Thus, the

Nernst equation with[ Mz⁺]= 10⁻⁶ mol/ l and T =298K
becomes
(c)

(d)

The value for the standard potential E°ᴍ/M+ ᴢ⁺ is given in Table

1, provided that the metal M is known.
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 2. Vertical line 2:

This reaction involves a fixed hydrogen concentration only; the

equilibrium constant Ksp for this reaction must be known so
that
(e)

Therefore, a straight line is drawn starting at E1-pH2 point. It

should be mentioned that the metal oxide MxOz can be
replaced by a metal hydroxide M(OH)₂ or M(OH)₃ depending
on the chosen metal.
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3. Incline line 3:

Notice that this reaction involves both hydrogen and

electron transfer. Then, the Nernst equation becomes

The standard potential Eᵒᴍ⁄ᴍxοz must be known. In Fig. 3,

line 2 and line 3 intersect at a pH₂ value given by Eq. (e).
Above this pH, a passivation process takes place on the
metal surface according to the following reaction
where MxOz is a passive film compound

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4. Vertical line 4:
(a)

(b)
(c)

Subsequently, a vertical line 4 is drawn at this pH4 value.

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 Table 1.
Standard
potential for
metal reduction

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 Fig. 5 Simplified Pourbaix diagram for copper-water
system showing domains of corrosion, immunity, and
passivation of copper (CU) at 25°C

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• The diagram shows stable species at standard conditions.
Notice that only two copper oxides, CuO and Cu₂O, form
in alkaline water environments. Moreover, a Pourbaix
diagramis a two-dimensional map in the metallic
corrosion space, summarizing the thermodynamic state
for immunity, corrosion, and passivity. The term passivity
represents a region where metal oxide or hydroxide
forms on a metal substrate as a thin coating for
protection against metal oxidation

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 Iron Pourbaix

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 Simplified Pourbaix diagram for
iron-water system showing domains
of corrosion, immunity, and
passivation of iron (Fe) at 25°C

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 Limitation of Pourbaix diagram
✓ The validity of the diagrams is limited to reactions
between pure metals, pure water
✓ and the species that can be formed from these. Small
amounts of impurities and alloying elements in the
metal and dissolved substances in the water do not
necessarily influence strongly on the diagram, but in
some cases they do.
✓ These diagrams are purely based on thermodynamic
data and do not provide any information on the
reactions.
✓ Consideration is given only to equilibrium conditions in
specified environment and factors, such as
temperature and velocity are not considered which
may seriously affect the corrosion rate.
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✓ Pourbaix diagrams deal with pure metals which are
not of much interest to the engineers.
✓ All insoluble products are assumed to be protective
which is not true, as porosity, thickness, and
adherence to substrate are important factors
✓ Although the above disadvantages appear to be
substantial, the advantages offered by the Pourbaix
diagrams far outweigh their limitations
✓ The activity of species is arbitrarily selected as 10-6
g/mol which is not realistic

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 Thermodynamics of Surfaces
What are surface, surface energy and surface tension?
✓ A surface is in fact an interface between two phases.
What we commonly call the surface of a solid is
actually the interface between the solid and the
surrounding air. We can similarly, have different
interfaces such as solid–liquid, liquid–gas or solid–solid
and liquid–liquid.
✓ surface energy is the excess energy at the surface of a
material compared to the bulk

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✓The formation of bonds between two atoms in a
solid is accompanied by a decrease in the
energy. As the atoms on the surface have fewer
bonds than the atoms in the bulk the
energy of the surface atoms is higher. The extra
energy associated with the surface atoms is
called surface energy.
✓ Surface tension is the tendency of fluid surfaces to
shrink into the minimum surface area possible.
Or it is surface energy per unit area

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✓ A simple estimate of surface energy, ϒ, can be made
by multiplying the number of bonds broken per
unit area, Nb, by one half of a bond energy e.

✓ Where na = number of atoms per unit area on the

surface and nb = number of bonds broken per atom.

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✓ Surface atoms are very different from atoms in the bulk.
✓ The fewer neighbors of the surface cause it to have a very
different and anisotropic chemical environment compared
with the bulk.
✓ The thermodynamics of the surface is most likely to be
quite different from the thermodynamic properties of the
bulk.
✓ Often certain atoms in multicomponent systems selectively
accumulate on the surface as a result of these properties
and impart rather different surface properties compared
with the bulk.
✓ The balance of energies at the surface is the reason why
small drops are curved and why liquid interfaces may rise
when placed in capillaries

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 Surface Thermodynamic Functions
Consider a large crystalline solid containing a total of N
atoms, which is bounded by surface planes. We can
determine various thermodynamic properties by including a
term that accounts for excesses from the surface properties.

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 Work Needed to Create A Surface area
Surface Tension: Surface area is increased by moving
atoms from the bulk to the surface and then to move surface
atoms out of the way to make room for the new surface
atoms.
✓ At const. T and P, the reversible surface work, dW, required
to increase the surface area, a, by an amount da of a one
component system is:

Where 𝛾 called “surface tension” and is two dimensional

equivalent of pressure. Note volume change is replaced with
change in the surface area.

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Contact Angles:-It is defined as the angle subtended
between the tangents drawn at the liquid surface and the
solid surface inside the liquid at the point of contact . The
angle of contact is determined by the nature of the liquid,
the solid with which it comes into contact, and the medium
that exists above the liquid's free surface.
✓ When a liquid is deposited on a surface, it may not form
a continuous film – wetting – but instead may break up
into droplets.
The shape of the droplets is defined by the relative surface
energies.
This is equally true for a solid drop forming from its melt on a
surface.

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Wetting and Spreading:- Wetting originates from the
adsorption of liquid molecules on the surface of particles. A
wetting process is actually a process in which a liquid and gas
compete for the surface of particles. It can be regarded as the
disappearance of the solid–vapor interface and formation of a
solid–liquid interface
The spreading parameter S is given by Wetting layer

S =  SV − ( SL +  LV )

✓ This coefficient determines whether a droplet forms, or

the surface is completely wetted.
✓ It is a measure of the difference in surface energy
between the substrate dry and wet.
✓ If S>0, the liquid spreads completely to cover the surface
and lower its surface energy:  is zero.

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✓ If S<0, partial wetting is said to occur, with a finite
contact angle.
✓ If the contact angle is 180o, the liquid forms a complete
sphere and the liquid is non-wetting.
Non-wetting

✓ In general, liquids will spread on highly polarizable

substrates such as metal and glass.
✓ They may or may not on plastics – if the liquid is less
polarizable than the substrate it will.

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 Adsorption
Adsorption is often described as a surface phenomenon where
particles are attached to the top layer of material. It normally
involves the molecules, atoms or even ions of a gas, liquid or
solid in a dissolved state that is attached to the surface.
Adsorption is mainly a consequence of surface energy
Adsorption Vs Absorption
The main difference is that while absorption involves the
mass transfer of particles into another material (one
substance absorbing another), adsorption takes place with
the adhesion of particles onto the surface of a susbtance.

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 Adsorbate:- refers to the molecular species that gets
adsorbed on the surface,
Adsorbent:- refers to the surface on which adsorption
happens.

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 Types of adsorption

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 Effect of Temperature on adsorption

a) physisorption b) chemisorption

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 Examples of adsorption Isotherm

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• Adsorption Equilibria

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 Adsorption isotherm

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 Basics of Adsorption Isotherm

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 Types of Isotherm

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 Langmuir isotherm
The Langmuir adsorption isotherm is used to describe the
equilibrium between adsorbate and adsorbent system, where
the adsorbate adsorption is limited to one molecular layer at
or before a relative pressure of unity is reached.

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 Limitation of Langmuir Adsorption Isothermal

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 Freundlich Adsorption Isotherm
The Freundlich Isotherm:- Adsorption is a physical chemical
process involving the mass transport of an adsorbate from the
solution phase (i.e., bulk solution, film, and intraparticle
transportation) to the interior surface of the porous
adsorbent where the adsorption occurs.

Basic
Assumption

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 Limitation of Freundlich Isotherm

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 Difference between Langmuir and Freundlich
adsorption isotherm

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 Brunauer–Emmett–Teller (BET)
Brunauer–Emmett–Teller (BET) theory is used to measure
the surface area of solid or porous materials. It gives
important information on their physical structure as the area
of a material's surface affects how that solid will interact
with its environment.
✓ BET theory applies to systems of multilayer adsorption,
and usually utilizes probing gases that do not chemically
react with material surfaces as adsorbates to quantify
specific surface area. Nitrogen is the most commonly
employed gaseous adsorbate used for surface probing by
BET methods

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 Drawback of BET

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 Application of BET
✓ Measure surface area of solid materials.
✓ It gives important information on their physical structure
as the area of a material's surface affects how that solid
will interact with its environment
✓ The inner surface of hardened cement paste
determination.

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 Assignments
1. Discuss Temkin isotherm and Dubinin-Radushkevich
isotherm
2. List and explain Types of BET Adsorption Isotherms in
detail

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 Solid Electrolyte
And
Defects In Solid Electrolyte
• Crystal defects
Crystalline solids consist of atoms, ions, and molecules
arranged in a strongly ordered microscopic arrangement in
consistent and repeated three-dimensional structures,
forming a crystal lattice that stretches in any direction.
A crystal defect is an interruption of the regular patterns of
arrangement of atoms or molecules in crystalline solids.

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Importance of crystal defects:- Defects determine
many properties of materials (those properties that we call
"structure sensitive properties").
✓ Even properties like the specific resistance of
semiconductors, conductance in ionic crystals or
diffusion properties in general which may appear as
intrinsic properties of a material are defect dominated.
✓ Plastic deformation of metals takes place mainly by
shearing. The material's lattice planes slide past each
other,
✓ allowing macroscopic shape change without significantly
changing the atom's ordering and arrangements.

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 Types of Defects in Solids
Defects in solids are classified into the following three
types:-
✓ Stoichiometric defects
✓ Non-Stoichiometric defects
✓ Impurity Defects
Stoichiometric defects are intrinsic/thermodynamic defects in
which the ratio of cations to anions remains exactly the same
as represented by the molecular formula.
These are further classified into two types
✓ Vacancy Defect: (Vacant sites in the lattice) in which an
atom is not present at its lattice sites causing that lattice
site to be vacant and create a vacancy defect.

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✓Interstitial Defect:- is a type of point crystallographic
defect where an atom of the same or of a different type,
occupies an interstitial site in the crystal structure

Vacancy defect Interstitial Defect

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The non-stoichiometric defect is the type of point defect,
and hence in this defect anion and cations are not equal in
proportion, and large numbers of negative and positive
charges are present.
Point defects:- are lattice defects of zero dimensionality,
i.e., they do not possess lattice structure in any dimension.
✓ The crystal defect where an equal number of cationic and
anionic vacancies are present is called the Schottky
defect.
✓ The crystal defect where some ions are displaced from
normal lattice sites to the interstitial sites is called the
Frenkel defect.

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 Defect chemical reaction
Reaction involving defects must be:-
✓mass balanced
✓- charge balanced: the effective charge must
✓ be balanced.
✓- site balanced: the ratio between
✓ anion and cation must remain constant

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 Thermodynamics of point defect
✓ The change in Gibbs energy can be expressed in terms of the
enthalpy of formation of each vacancy, ∆H, and the entropy
associated with the formation of the defects, ∆S.
✓ The entropy change can be divided into two parts:
i) a configurational entropy, ∆Sconf, arising from the
distribution of n vacancies among N+nV sites and
ii) A vibrational entropy, ∆Svib, due to the change in vibrational
modes of the atoms neighboring each vacancy.
The enthalpy and vibrational entropy changes reflect
actually not only the formation of the vacancy, but also
the terms resulting from the formation of a new site.
They may thus be taken as the energies required to form
the vacancy plus the energies required to form the new
site
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✓ The change in Gibbs free energy associated with the formation of nv
vacancies may accordingly first be written

Configurational entropy is the portion of a system’s

entropy that is related to discrete representative positions
of its constituent particles. It may describe the numerous
ways the atoms or molecules in a mixture can pack
together. Here, the mixtures can be alloy, glass or any other
solid substance. Moreover, this term can also refer to the
number of conformations of a molecule or the number
of spin configurations in a magnet as well. Therefore, this
term suggests that it may refer to all possible configurations
of a system.

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✓ Vibrational/Thermal entropy is an extensive property of a
thermodynamic system. Some things happen
spontaneously, others do not. For example, heat will flow
from a hot body to a cooler one, but we cannot observe
the opposite even though it does not violate the law of
conservation of energy. When a change occurs, the total
energy remains constant but is parcelled out differently.
Thus, we can determine the direction of change by the
distribution of energy. Also, a change is spontaneous if it
leads to greater randomness and chaos in the universe as a
whole. And, we can measure the degree of chaos,
randomness, or dispersal of energy by a state function; we
name it as the entropy.

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Figure : Example of the v
ariation in enthalpy, vibr
ational and configuration
al entropy, and Gibbs
energy with the concentra
tion of vacancies in an el
emental solid.

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