UNIVERSITY OF ENGINEERING & MANAGEMENT, KOLKATA

Course Name : Chemistry (Use of free energy in chemical

equilibrium_Module 5 )

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UNIVERSITY OF ENGINEERING & MANAGEMENT, KOLKATA

Thermodynamics

Electrochemistry

Water & corrosion

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 Thermodynamics is concerned with the flow

of heat

 It deals with the relationship between work

and heat

 It is applied in studying energy changes

associated with various physical and chemical
process
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System: A system may be defined as any specific

portion of matter under study which is separated
from the rest of the universe with boundary surface.

Universe = System + Surrounding

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Open System: Mass and energy can be

transferred through the boundary (e.g. an open
beaker to which we can add water)
Closed System: Energy exchange with the
surrounding but no mass transfer (you can cool a
closed water bottle in fridge)
Isolated System: Incapable of exchanging both
energy and matter (A closed thermos flask can be
considered as isolated).
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Classification of chemical systems

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Properties are of two types:

Extensive Properties: The property of a

system which depends on the amount of
substance is called extensive property. (volume,
energy, number of moles, etc.)

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Intensive Properties: The property which is

independent in the amount of substance
present in the system. (temperature, pressure,
density, sp. gravity, sp. Heat, dielectric
constant, viscosity , surface tension,
refractive index, etc. )

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Processes and Cycles

Any change a system undergoes from one
equilibrium state to another is called a process and
the series of states through which a system passes
during a process is called a path

To specify a process,
initial and final states and
path must be specified.

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State function
 Do not depend on the path by which the
system arrived at its present state
 internal energy, entropy or enthalpy and so
on

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Path function
 Depend on the path by which the system
arrived at its present state
 Work done etc.

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Reversible process: In a reversible process the

change of the system is allowed to happen slowly
in minute quantities. In ideally reversible
process the change must occur in successive
stage of infinitesimal quantities.

The magnitude of change of the thermodynamic

quantities in the different stage will be the same,
and opposite sign in the forward and backward
direction.
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Irreversible process: Such process occurs

suddenly or spontaneously without the
restriction of the occurring in successive stage of
infinitesimal quantities.

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Work done in a process

In thermodynamics we generally consider
mechanical work, i.e., PV type work.

𝑊𝑜𝑟𝑘=𝐹𝑜𝑟𝑐𝑒 ×𝐷𝑖𝑠𝑝𝑙𝑎𝑐𝑒𝑚𝑒𝑛𝑡

A gas was contained in a cylinder fitted with a

frictionless piston and the temperature is constant
(T). If we want to calculate the work done due to
expansion of the gas from V1 to V2 volume:
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Work done in reversible process

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Fig. 1

Let the pressure P on the piston be exactly equal to

the pressure of the gas within. The piston will
neither move downward nor upward (Fig. 1a)

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Ref: Puri Sharma Pathania Physical Chemistry Book
 UNIVERSITY OF ENGINEERING & MANAGEMENT, KOLKATA

Fig. 1

Now, the pressure on the piston is decreased by an

infinitesimally small amount dP. Hence, the piston
will move up and the gas will expand by an
infinitesimally small amount (reversible manner)

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Work done in irreversible process:

𝑊=𝑃(𝑉2−𝑉1)

Convention of work:

Work = -Ve for work done by the system,

expansion of gas.

Work = +Ve, work done on the system,

compression of gas. 19
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Fig. 1

Pressure on the piston (external pressure), is made

much smaller than the pressure of the gas within
the cylinder, then the gas will expand rapidly,
pushing the piston upward suddenly (irreversibly)

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Ref: Puri Sharma Pathania Physical Chemistry Book
 UNIVERSITY OF ENGINEERING & MANAGEMENT, KOLKATA

Types of chemical reactions

Chemical reaction

Exothermic Endothermic
Heat is liberated into the Heat is absorbed from
surroundings the surroundings
H0 H  0
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Processes in Thermodynamics:
Isothermal process: If a change takes place in such
way that temperature remains constant throughout,
is called isothermal process (dT=0).
Adiabatic process: A process is said to an adiabatic,
if no heat enters or leave the system during any step
of the process (i.e., dq=0).
Isobaric process : At constant pressure.
Isochoric process : At constant volume.
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Temperature
 The concept of temperature springs from the
observation that a change in physical state can
occur when two objects are in contact with one
another as when a red-hot metal is plunged into
water.
 Change in state can be interpreted as arising from
a flow of energy as heat from one object to another.

 The temperature, T, is the property that

indicates the direction of the flow of energy
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Ref: Atkins' Physical Chemistry - Oxford University Press
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 If energy flows from A to B when they are in contact, then

we say that A has a higher temperature than B.

Thermal equilibrium is established if no change of state

occurs when two objects A to B are in contact through a
diathermic boundary.
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Ref: Atkins' Physical Chemistry - Oxford University Press
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This observation is summarized by the Zeroth Law

of thermodynamics:

If A is in thermal equilibrium with B, and B is in

thermal equilibrium with C, then C is also in
thermal equilibrium with A

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First law of thermodynamics

The amount of heat produced is proportional to
the work spent or conversely, if heat is transferred
into work, there is proportionality between the
work obtained and heat disappeared.

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First law of thermodynamics

Law of conservation of energy
 Energy can neither be created nor be
destroyed.
 When some form of energy disappears an
exactly equivalent amount of energy of some
other form makes its appearance.
 Total energy of the Universe is constant.
Mathematical form: 𝑑𝑞= 𝑑𝑢+𝑤
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Internal energy (U)

The energy possessed by a system by virtue of
its existence, is known as internal energy (U).
It is contributed by different molecular motion
and non-bonding interactions, such as
vibrational, rotational, electric energy etc.
1. It is an extensive property.
2. It is a state function.
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𝒅𝒒= 𝒅𝑼+ 𝑷𝒅𝑽 [only mechanical work

involved]

Now, if the process occurs at constant volume,

then 𝑑𝑉=0, so 𝑃𝑑𝑉=0

We can write 𝒅𝒒𝑽=𝒅𝑼 𝒐𝒓,

𝒒𝑽=𝜟𝑼 (This is the physical significance of 𝑞𝑉)
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Enthalpy
The term Enthalpy (Heat content) is the total
energy content of a system by which it can do
the work.
For solids/liquids, H = U ?
For gas: 𝑼+𝑷𝑽= 𝑯, where H is enthalpy
1. It is an extensive property.
2. It is a state function.
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We know, 𝑯 = 𝑼+𝑷𝑽 , ∴ 𝒅𝑯 = 𝒅𝑼 +𝑷𝒅𝑽 +𝑽𝒅𝑷

If the change occurs at constant pressure,
then 𝑑𝑃=0,𝑉𝑑𝑃=0
Then, 𝒅𝑯=𝒅𝑼+𝑷𝒅𝑽
From 1st law of thermodynamics, 𝒅𝒒=𝒅𝑼+𝒑𝒅𝑽
(only mechanical work involved)
So that , 𝒅𝑯=𝒅𝒒𝑷 and 𝒒𝑷=𝜟𝑯 (This is the physical
significance of 𝒒𝑷)
So change in enthalpy is nothing but heat
content of the process at constant pressure. 32
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Heat capacity
Heat capacity of the system is define as the
quantity of the heat is required to raise the
temperature of the system from the lower to
the higher temperature divided by the
temperature difference.

𝑪=𝒅𝒒/𝒅𝑻

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Heat capacity at constant pressure:

As we know that 𝒅𝑯=𝒅𝒒𝑷

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Heat Capacity at Constant Volume

As we know that 𝒅𝒒𝑽=𝒅𝑼

Cp > Cv for gases

For solids or liquids Cp ≈ Cv ?
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Cp Cv = R
dq = dU + dW
dU = Cv dT and dq = Cp dT
Therefore CP dT = CV dT + PdV
For ideal gas PdV = nRdT
So, CP dT = CV dT + nRdT
So, (CP  CV) dT = nRdT
CP  CV = nR
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Thermochemistry
Thermochemistry is the study of the energy
transferred as heat during the course of chemical
reactions .
Calorimetry is used to measure the energy
supplied or discarded as heat by a reaction, and
can identify q with a change in internal energy.

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Conversely, if we know U for a reaction, we

can predict the energy (transferred as heat)
the reaction can produce.
A process that releases energy by beating the
surroundings is classified as exothermic and
one that absorbs energy by cooling the
surroundings is classified as endothermic.
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CARNOT CYCLE
Carnot's theorem, developed in 1824 also
called Carnot's rule, is a principle that specifies limits
on the maximum efficiency any heat engine can obtain

The Carnot’s engine is nothing but one mole of an ideal

gas enclosed in a cylinder, fitted with a weight less and
friction less piston. There are two reservoirs, one at high
temperature Th (source) other at low temperature Tc (sink).
Now the following cyclic process consisting of four steps is
performed.
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CARNOT CYCLE

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For the ideal case of the Carnot cycle, efficiency can

be written

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Practice at Class
1. Five mole of ideal gas expands reversibly from an initial pressure 10 atm. to a
final of 0.4 atm.; the temperature being kept constant at 0C. How much work is
done by the gas? What is the change in U and H? How much heat is absorbed?

2. For a certain ideal gas what will be the maximum work performed in the
expansion of 2 moles of the gas from 4 to 40 liters at 300 K?

3. 1 mole of ideal monoatomic gas (CV = 3/2R) initially at 0C experiences a

reversible compression process in which U is 900 Cal. and q is 400 Cal.
Calculate final temperature and W.

4. Heat supplied to a Carnot engine is 2000 kj. How much useful work
can be done by the engine which works between 0°C and 120°C?
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Entropy
It is the measure of randomness or
disorderliness at the molecular level of the
system and denoted by S.
It is an extensive property and state
function.

Ssys +Ssurr = 0 for reversible process

Ssys +Ssurr > 0 for irreversible process
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Entropy change for an ideal gas

I. Temperature and volume as variables:

II. Temperature and Pressure as variable:

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I. Temperature and volume as variables:

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II. Temperature and Pressure as variable:

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II. Temperature and Pressure as variable:

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Case 1: In case of isothermal process, 𝑑𝑇=0

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Entropy and disorderliness

 Factors responsible for spontaneity of a
reaction

I. Tendency for minimum energy

II. Tendency to attain maximum randomness
(entropy)

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 Entropy of universe
A system absorb heat from surroundings or release
heat to surroundings both system and surroundings
undergo change in entropy.
Heat change of surroundings is equal but the negative
of the heat change of the system in reversible process.

qsys =  qsurr
Suniverse= Ssys+ Ssurr = 0

Entropy change in reversible process for universe

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For an irreversible (spontaneous) process

the Ssurr = qirrev/T
Suniverse = Ssys  qirrev/T
= qrev/T  qirrev/T >0

For an irreversible process for universe the net

entropy increases or
Entropy of the universe is increasing since
spontaneous reactions are always taking place in
universe.
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Incompleteness in the First Law

 First law does not tell about the direction of
heat flow or energy transfer.

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To Illustrate:
Fluid always flows from higher to lower
elevation spontaneously.
Heat always flows from high to low
temperature spontaneously.
 Material always diffuse from high to low
concentration spontaneously.

And reverse of these processes never happen

naturally (without aided by any external agency)
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The recognition of two classes of process,

spontaneous and non-spontaneous, is
summarized by the Second Law of
Thermodynamics.
The second law of thermodynamics is formulated to
record our experiences about direction of change,
stated as
All spontaneous processes are irreversible.
All spontaneous processes tend to equilibrium.
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Second law of thermodynamics

1. “It is impossible to take heat from a

hotter reservoir and convert it absolutely
into work by a cyclic process without
transferring a part of heat to the cooler
reservoir”- Kelvin Statement

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Second law of thermodynamics

2. “It is impossible for a cyclic process to
transfer heat from a body at a lower
temperature to one at higher temperature
without at the same time converting a
portion of work to heat” –Clausius Statement
3. The total entropy of the universe tends to
increase always.

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Spontaneous processes are those that can

proceed without any outside intervention and
spontaneous in one direction are
nonspontaneous in the reverse direction.

Water
Ice

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Free energy
The thermodynamic functions which consider both
energy and randomness together are known as
free energy functions
1. Gibb’s Free EnergyG = H – TS
2. Helmholtz free energy F or A = U – TS

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Condition for spontaneity of a process

By knowing the change of free energy we can
predict the process is carried out by reversibly or
spontaneously.

We know, G = H - TS
Or dG = dH – TdS – SdT ………… (1)

Again, we know H = U + PV
Or, dH = dU + PdV + VdP …………… (2)
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So putting the value dH in equation (1), then

dG = dU + PdV + VdP – TdS - SdT
If the process is carried out at constant T and P
𝑑GP,T = 𝑑U + PdV – TdS
Now if the system performs mechanical work only so from
1st law of thermodynamics we can write 𝑑𝑞 = 𝑑𝑈 + 𝑃𝑑𝑉
𝑑GP,T = 𝑑q – TdS ………… (3)
We know dS = dqrev / T,  TdS = dqrev
Now putting the value of TdS in equation (3), Then
𝑑GP,T = 𝑑q – dqrev 61
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1. If the process is reversible then 𝑑𝐺P,𝑇 = 𝑑𝑞𝑟𝑒𝑣 − 𝑑𝑞𝑟𝑒𝑣

For reversible process: 𝑑𝐺𝑃,𝑇=0

2. If the process is irreversible then 𝑑𝐺𝑃,T = 𝑑𝑞𝑖𝑟𝑟 − 𝑑𝑞𝑟𝑒𝑣

It is already known that 𝑑𝑞𝑟𝑒𝑣 > 𝑑𝑞𝑖𝑟𝑟

So, 𝑑𝐺𝑃,𝑇 < 0 (for irreversible/spontaneous process)

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Electrochemistry and
Electromotive force

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Oxidation: Loss of electron(s) by any species.

Reduction: Gain of electron(s) by any species.

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Electrolytic cell: Convert electrical energy

into chemical energy.
Example : Electrolysis of water, Electrolysis of NaCl to synthesize Na
metal, Al-metal from baxuite, Electroplating of Au, Recharging of
batteries

Electrochemical cell: Convert chemical

energy into electrical energy.
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Galvanic cell: A galvanic cell is a device in

which the free energy of a chemical process
is converted into electric energy.

When the electrodes are externally connected

by a metallic wire, current flows from one
electrode to the other and inside the cell
chemical changes occur at the surface of the
electrodes.
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The Daniell cell is a type of electrode

chemical cell, consists of Zinc (Zn) rod
partially immersed in ZnSO4 solution and a
Copper (Cu) rod in CuSO4 solution.

The two solutions are separated by a porous

barrier which allows the current to pass
through but prevents mass diffusion.

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During production of current, Zn atoms pass

into solution as Zn2+ leaves behind two electrons
each into the metal electrode. On the other hand
Cu2+ ions from the solution are deposited on the
Copper (Cu) electrode by accepting 2 electrons.

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Daniel cell

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Cell potential (EMF of the cell)

In an electrochemical cell the potential difference

across the electrodes operates as a driving force
for the flow of electrons and thereby current and
is known as cell potential/electromotive force
(EMF).

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In a cell one-mole of metal M (Valency = n)

oxidize in a given time, then within this time
nF Coulomb will flow in the external circuit. If
‘E’ is the EMF of the cell then electrical 𝑊𝑜𝑟𝑘
= 𝑛𝐹𝐸
Since electric work is net work, then we can
write: −𝛥𝐺 = 𝑛𝐹𝐸 𝑜𝑟, 𝛥𝐺 = −𝑛𝐹𝐸
-dG = Wmax – PdV = Max work – mechanical work = NET work
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 Prove 𝛥𝐺 = - 𝑛𝐹𝐸
We know, G = H – TS ( G is a state function,
perfect differential and exothermic parameter)
G = U + PV – TS ( As, H = U + PV)
To understand the meaning of G, Let us differentiate the
above equation,
dG = dU + PdV + VdP – TdS - SdT ……(1)

From 1st law of thermodynamics; dqrev = dU + Wmax

As, dS = dqrev/T So that, TdS = dU + Wmax
We can rewrite the Equ. (1);
dG = PdV + VdP – Wmax - SdT
 So we have dG = PdV + VdP – Wmax - SdT
dGP,T = PdV – Wmax
So that, -dGP,T = Wmax - PdV = Wnet

Hence decrease in Gibbs Potential at constant P

& T gives us NET WORK obtainable from the
system.
As we know electrical work = nFE, since
electrical work is net work.
Now, we can write −𝛥𝐺 = 𝑛𝐹𝐸 𝑜𝑟, 𝛥𝐺 = − 𝑛𝐹𝐸
 Oxidation-Reduction potential
The tendency of an oxidant is called its reduction
potential. Higher the reduction potential of a
couple, higher will be its oxidizing power.
A couple with higher reduction potential value
will always oxidize a couple which have lower
reduction potential value.

Since the reduction potential value of

Ce4+│Ce3+ couple is greater than Fe3+│Fe2+
couple, so Ce4+ is stronger oxidant that Fe3+.
UNIVERSITY OF ENGINEERING & MANAGEMENT, KOLKATA
Electrochemical series:

Electrochemical
series is a series of
chemical elements
arranged in order
of their standard
electrode
potentials.

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Derivation of Nernst Equation

Let us consider a cell reaction

In order to analyze a chemical reaction, we form this

reaction coefficient.

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Applying Van’t Hoff reaction isotherm,

ΔG = ΔG0 + RT ln Q (Q is the reaction coefficient)

We know ΔG= -nFE and ΔG0 = -nFE0

Dividing both sides by –nF,

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In general, the Nernst Equation is

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Solved Problems
1. Calculate E and G for the reaction, Cr2+ + 2e-  Cr (s)
at 298K, Given: Cr3+ +3e-  Cr (s); E = 0.50V, and Cr3+ + e-
 Cr2+; E = - 0.410V.
The reactions can be arranged as
Cr3+ +3e-  Cr (s); E = 0.50V
Cr2+  Cr3+ + e- ; E = + 0.410V.
The final reaction coming as, Cr2+ + 2e-  Cr (s)
Ecell = Ereduction + Eoxidation
Ecell = 0.50 + 0.41 V
Ecell = 0.91 V
G = -nFE
G = - 2x 96486x0.91 J/mole 82
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2. Calculate the emf of a Daniel at 25C, when the

concentration of ZnSO4 and CuSO4 are 0.001M and 0.1M
respectively. The standard electrode potential of cell is
1.1V.
The reaction of daniel cell
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

Now standard electrode potential of cell is 1.1V. Then,

E cell = 1.1 – (0.059/2 )log(0.001/0.1)
= V? 83
 Hardness of Water
The property of water to form an insoluble curd with
soap instead of lather. In other words it is the soap
destroying property due to the presence of
Bicarbonates, Sulphates and Chlorides of Calcium
and Magnesium.
Types of Hardness
A. Temporary Hardness: It is due to the presence of
Bicarbonates of Calcium & Magnesium and can be
removed by boiling.
Eg: Ca (HCO3)2 → CaCO3 + CO2 + H2O
B. Permanent Hardness: It is due to the presence of
sulphate, nitrates and chlorides of Calcium &
Magnesium and it cannot be removed by boiling.
 Determination of Hardness
The hardness of water can be estimated by
methods such as Gravimetric analysis, EDTA
titration, Atomic absorption, etc.,
EDTA titration is the most inexpensive and
simple way of determining the hardness.
Permanent hardness is usually determined
by titrating it with a standard solution of
EDTA (complexing/chelating agent used to
capture the metal ions)
 First the EDTA soln. is standardized by
titrating it against a standard solution and its
normality is found out.
 Then the total hardness is found out by
titrating the water sample(added buffer soln.
and EBT indicator) against the standardized
EDTA solution.
 Temporary hardness is found by subtracting
the permanent hardness from the total
hardness.
 EBT

EDTA – Metal complex

Ca2+ + EBT → [Ca-EBT] (Unstable complex of Wine red)

[Ca-EBT] + EDTA → [Ca-EDTA] (Colorless) + EBT (Blue)

 Corrosion
Corrosion of metals is defined as the spontaneous
destruction of metals in the course of their
chemical, electrochemical or biochemical
interactions with the environment. Thus, it is
exactly the reverse of extraction of metals from
ores.
Example: Rusting of iron: A layer of reddish scale
and powder of iron oxide is formed on the surface
of iron metal.
A green film of basic carbonate [CuCO3 +
Cu(OH)2] is formed on the surface of Cu, when it
is exposed to moist-air containing carbon dioxide.
CLASSIFICATION OF CORROSION
(i) Dry or Chemical Corrosion
(ii) (ii) Wet or Electrochemical Corrosion
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