Electrochemistry

ELECTROCHEMISTRY
What is Electrochemistry?
•Electrochemistry is the branch of chemistry concerned
with the interrelation of electrical and chemical changes
that are caused by the passage of current .
•It is the study of chemical reactions which take place at
the interface of an electrode (solid, metal or
semiconductor) and an ionic conductor (electrolyte).
•It deals with the interaction between electrical energy and
chemical change.
Such reactions are broadly classified into two categories:
•Production of chemical change by electrical energy i.e. the
phenomenon of electrolysis
•Conversion of chemical energy into electrical energy. i.e.,
the generation of electricity by spontaneous redox
reactions.
Electrochemical cell
An electrochemical cell is a device that can generate
electrical energy from the chemical reactions occurring in
it, or 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 - There are two types of electrochemical cells:
Galvanic cells also called Voltaic and Electrolytic cells.
Galvanic cell - example - Daniel cell
A galvanic cell is an electrochemical cell, used to supply
electrical current by making the transfer of electrons
through a spontaneous redox reaction. During redox
reactions, the galvanic cell converts chemical energy into
electrical energy by transferring energy between the
electrons.
Electrolytic cell
An electrolytic cell converts electrical energy into
chemical energy. In this cell redox reaction is not
spontaneous, and electrical energy required to initiate
the reaction. It involves non-spontaneous reactions and
thus require an external electron source like a DC
battery or an AC power source.
EMF
The electromotive force or EMF of a cell is the
maximum potential difference between two electrodes
of a cell. It can also be defined as the net voltage
between the oxidation and reduction half-reactions.
The EMF of a cell is mainly used to determine whether
an electrochemical cell is galvanic or not.
Source:Digital Kemistry. https://i.ytimg.com/vi/cNs7CPevcYs/maxresdefault.jpg
Electrode
An electrode by definition is a point where current enters
and leaves the electrolyte. When the current leaves
the electrodes it is known as the cathode and when the
current enters it is known as the anode. Electrodes are
vital components of electrochemical cells.
Salt bridge
Salt bridge is usually an inverted U- tube filled with a
concentrated solution of inert electrolytes. It is used to
maintain the charge balance and to complete the circuit
by allowing the flow of ions through it. It contains a gel in
which inert electrolytes like KNO3 or K2SO4 are mixed.
Through the salt bridge, negative ion flows towards the
anode and positive ion flow to the cathode and the charge
balance is maintained and cell keeps on functioning..
Electrolyte
An electrolyte is a substance that produces an
electrically conducting solution when dissolved in a polar
solvent, such as water. A substance that dissociates into
ions in solution acquires the capacity to conduct
electricity. Sodium and potassium chlorides, calcium and
magnesium phosphates are examples of electrolytes.
Potential
The cell potential of an electrochemical cell is
the potential difference occurring between the two
electrodes of the cell, and arises due to the transfer of
electrons through the external circuit of a cell that has
not reached equilibrium
ORIGIN OF
POTENTIAL
At anode (oxidation half)
Zn(s) →Zn+2 + 2e–
At cathode( reduction half)

Cu+2(aq) + 2e– → Cu(s)
Overall reaction
Zn(s) + Cu+2(aq) → Zn+2 + Cu(s)
• Electrode potential: This tendency of losing of

electrons (oxidation) or gaining of electrons (reduction)
is called electrode potential.
• Unit for electric potential is expressed in joules per
coulomb (i.e., volts), and differences in potential
energy are measured with a voltmeter.
Current
When there is a potential difference between two
points in a conductive medium, electric charge
starts flowing from the higher potential point to
the lower potential point to balance the charge
distribution between the points. The rate of flow of
charge in respect of time is known as electric
current.
If Q Coulomb electric charge gets transferred

between these two points in time t sec, then the
current can be calculated as
I=Q/t
The electric current is the rate of flow of electric
charge through a conducting medium with respect
Coulomb is the quantity of electricity
when 1 ampere is passed through a load
for one second.
Q = As
Electric power, Watt = VA
Consumption of electricity, Units of
electricity = one Kwh (when one
kilowatt power is consumed for one hour)
Energy term Joule is related to electrical
potential by
Joule=Volt coulomb = Volt Ampere
second VAs = Watt second
1HP = 750 watts
Faraday’s Law of Electrolysis
The relationship between the quantity of

electric charge passed through an electrolyte
and the amount of substance deposited at the
electrodes was given by Faraday in 1834, in
the form of the law of electrolysis.
Faraday’s constant (F) – It is the charge

possessed by 1 mole of electrons and it is
equal to 96500 coulombs(approx.). In terms of
Faraday’s constant the number of gram
equivalent of electrolyte discharged at an
electrode is equal to the faraday’s passed.
F = Avogadro's Number × charge on electron in
coulombs
= 6.022 × 1023 mol-1 × 1.602192 ×
10-19 C
= 96,484 C mol-1
(usually rounded up to 96,500 C mol-1 )
F is equal to the quantity of electricity carried by one

mole of electrons
Q = n(e-) × F
Q = quantity of electricity measured in coulombs (C)
n(e-) = moles of electrons used
F = the Faraday (Faraday constant) = 96,500 C mol-1
1 mol electrons = 6.023×1023 electrons (Avogadro's
number)
No of electrons = Q X 6.023×1023
Faraday’s First Law
When an electric current is passed through an electrolyte,
the amount of substance deposited is proportional to the
quantity of electric charge passed through the electrolyte.
If m is the mass of the substance deposited by passing Q
coulomb of charge then according to this law:
m∝Q
Now, Q = I ✕ t
m∝I✕t
m=Z✕I✕t
M=ZXQ
Where Z is a constant known as electrochemical
equivalence and is characteristic of a substance
deposited. It is the mass of the substance in grams
deposited or liberated by passing one coulomb of charge.
Faraday’s Second Law
When the same quantity of charge is passed through different
electrolytes, then the mass of different substance deposited
at the respective electrodes will be in the ratio of their
equivalent masses.
Mathematically it is represented as;
W1 / W2 = Z1 / Z2
Where W1 and W2 are the weight of two substances which are
deposited at their respective electrodes and Z1 and Z2 are
their respective equivalent weight.
Source:https://
www.periodni.com/
gallery/
faraday_laws.png
Faraday’s second law can be explained by
taking an electrolytic cell for depositing copper
from copper sulphate solution placed in series
with another for depositing silver from silver
nitrate solution.
Since the two cells are in series the same current

flows through both.
According to faraday’s second law, one faraday

liberates one gram equivalents of both silver and
copper.
96,500 coulombs deposit 107.87 g of silver and

31.77g of copper.
Problem: A constant electric current
deposit 365mg of silver in 216min
from an aqueous solution of silver
nitrate. What is the quantity of
current?
Ans. AgNO3 + e-  Ag
96,500 C deposits 108
g of silver
Therefore 365 х10-3 g of silver
deposited by 326 .13 C
The amount of current used is 25.16
mA
number of electrons flowing in the cell per second (ii) weight of
silver deposited.
Solution
(i) Quantity of current passed = It
= 0.2AX30X60
= 360 C or 360 As
No of electrons = Q X 6.023×1023
F
= 360 C X
6.023X1023
96500 C
= 2.2469 X 1021
electrons
No. electrons flowing per second = 2.2469 X 1021 /30 x 60
= 1.2483 X 1018
(ii) Ag+ + e- Ag
1mole of electron in a balanced equation refers to 1 F of electricity
1F of electricity are used to deposit 108 g of Ag
For passing 360 C of electricity the weight of Ag deposited =
108gX360C
Problem: A solution of CuSO4 was electrolyzed with a
current of 2.5A for 3 hours. Calculate (i) the weight of
copper deposited on a Pt square cathode of sides 5cm and
(i) the thickness of the deposit.(Density of copper =
8.92cm3; Atomic weight of copper = 63.55g)
.
Solution:
•Weight of Cu deposited
Quantity of current passed = It
= 2.5X3X60X60
= 27000C
Cu++ + 2e- Cu
2moles of electron in a balanced equation refers to 2F of
electricity
2F of electricity are used to deposit 63.55g of Cu
For passing 27000C of electricity the weight of Cu
deposited = 63.55gX27000C
2X96500C
=
8.89g
Area of the square cathode = (5cm) 2 X2faces =
50cm2
Volume of Cu deposited = Mass of Copper
Density of Copper
= 8.89cm2/8.92cm3 = 0.9966
cm3
•Thickness of the deposit

Thickness of the deposit = Volume of Cu deposited
Area of the square cathode
= 0.9966cm3
50cm2
= 0.0199cm = 199 microns

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At cathode( reduction half)

• Electrode potential: This tendency of losing of

If Q Coulomb electric charge gets transferred

The relationship between the quantity of

Faraday’s constant (F) – It is the charge

F is equal to the quantity of electricity carried by one

Since the two cells are in series the same current

According to faraday’s second law, one faraday

96,500 coulombs deposit 107.87 g of silver and

•Thickness of the deposit

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