Physical Chemistry II

Fundamentals of electrochemistry-Lecture 2

Jerry A Fereiro

16th Aug -2022

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School of Chemistry – IISER TVM
 Fundamentals of electrochemistry
This conversion takes place in an electrochemical cell

Standard Hydrogen electrode Saturated calomel electrode Ag/Agcl electrode

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 Standard Reduction Potentials
Cathode
(Reduction)

(Anode)
Oxidation

When you hear the term electrode potential, by convention it means reduction potential (potential or tendency to undergo
reduction). That is why if the E° value is positive, the tendency to undergo reduction is high. If it’s negative it means the
tendency to undergo reduction is low, ie, tendency to oxidize is high. 3
 Fundamentals of electrochemistry
This conversion takes place in an electrochemical cell

1) Galvanic cell
2) Electrolytic cell

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 Electrolytic cells

➢ Imagine reversing the direction of spontaneous reaction in a galvanic cell through the input of electricity

➢ Electrolysis is used to drive an oxidation-reduction reaction in a direction in which it does not occur spontaneously.

Though the direction of electron flow in electrolytic cells may be reversed from the direction of spontaneous electron flow
in galvanic cells, the definition of anode and cathode remain the same – reduction takes place at the cathode and
oxidation takes place at the anode.
Demonstration of Galvanic and Electrolytic cells
with one example
 Difference between Galvanic and Electrrolytic cell

Galvanic Cells Electrolytic Cells

Spontaneous redox reactions convert the chemical Non-spontaneous redox reactions convert the electric
energy to an electric energy energy to a chemical energy

Electric energy is generated by redox reactions Electric energy brings about the chemical reaction with
the help of an external source

The cathode is the positive electrode and anode is the The anode is the positive electrode and cathode is the
negative electrode negative electrode

The process of oxidation takes place at the anode and the Here, the oxidation process occurs at the anode while the
reduction process occurs at the cathode reduction process takes place at the cathode

Half cells are set up in different containers and are Electrodes are kept in the same container in a molten or
connected through salt bridges solution electrolyte

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 Some technologies based on electrochemistry
Energy storage
Sensors
Electroplating Corrosion

Energy conversion

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 Electrochemical process in nature
Cellular respiration Charge transfer processes Photosynthesis

“Life is nothing but an electron looking for a place to rest”

Albert Szent-Györgyi
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(Nobel Prize 1937)
Electroplating

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 Practical Charging – Discharging strategy

➢ During charging electrical energy is converted into chemical energy

The charging is conducted by applying an external voltage of opposite polarity to that of discharging in order to gain
Higher total cell potential

➢ During discharge, chemical energy is converted into electrical energy

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Faraday’s Laws of Electrolysis
Michael Faraday extensively studied electrolysis and established a relationship between the amount of substance
deposited at the electrode and the quantity of electricity passed through the electrolyte. He formulated two quantitative
laws that simplify the calculations based on electrolysis.

Faraday’s 1st law of Electrolysis

According to the law, the weight of metal deposited at the cathode is directly proportional to the quantity of electricity
used.
W∝Q
W= ZQ
Since Z = Electrochemical equivalent = Equivalent weight/ Faraday’s constant (Faraday’s Constant= 96500)

Faraday’s 2nd law of Electrolysis

According to the second law, if the same electricity (in terms of quantity) is passed through different electrolytes that stay
connected in series, then the weight of metal deposited at the cathode is directly proportional to its equivalent weight.

W ∝ Eq wt
w1 / w2= E1 / E2

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Nernst Equation
The Nernst equation provides a 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.

Derivation of Nernst equation

Change in the Gibbs free energy is equal to the maximum useful work done in a process.

Change in Gibbs free energy ΔG = charge passed X potential difference

According to the theory of thermodynamics, Gibbs free energy under general conditions can be related to Gibbs free
energy under the standard condition and the reaction quotient as:
ΔG=ΔGo + RT lnQ

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 The Nernst Equation
The Nernst Equation calculating the non-
standard cell potential
aA + bB cC + dD

[C] c
[D] d
ΔG = ΔGo + 2.303RT log and Δ G = −nFE
[A] [B]
a b

[C] c
[D] d

− nFE = −nFE o + 2.303RT log

[A]a [B]b

c d
2.303RT [C] [D]
E =E −o
log
nF [A]a [B]b

0.0592 [C] c
[D] d
E = Eo − log at 25 o
C
n [A] [B]
a b
 Reversibility
If a system follows Nernst equation, the electrode reaction is often said to be thermodynamically or
electrochemically reversible

Electrostatics Thermodynamics

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 Difference between two and three electrode cells

❖ The electrode at which the reaction of interest occurs is called the working electrode. The potential of the working electrode is
varied with time

❖ A second electrode, called the reference electrode maintains constant potential due to its constant composition

❖ The electrode at which the other (coupled) reaction occurs is called the counter electrode

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Difference between two and three electrode cells

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 Working principle of 3 electrode system

❑ Surface area of the counter electrode should be larger than the working electrode surface so the reaction can occur fast
enough and not limit the process on the working electrode.

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3 electrode system connections in real world

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