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Electrochemistry

Electrochemistry studies the conversion of chemical energy into electrical energy and vice versa, involving electrochemical reactions such as those in batteries and electrolysis. Key concepts include electrode potential, standard electrode potential, and the Nernst equation, which relates cell potential to concentration. Applications of electrochemistry include battery technology, electroplating, and metal purification.

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23 views12 pages

Electrochemistry

Electrochemistry studies the conversion of chemical energy into electrical energy and vice versa, involving electrochemical reactions such as those in batteries and electrolysis. Key concepts include electrode potential, standard electrode potential, and the Nernst equation, which relates cell potential to concentration. Applications of electrochemistry include battery technology, electroplating, and metal purification.

Uploaded by

Prashant Rai
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© © All Rights Reserved
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What is Electrochemistry?

• Electrochemistry is the study of production of electricity from energy


released during spontaneous chemical reactions and the use of electrical
energy to bring about non-spontaneous chemical transformations.
• If a chemical reaction is driven by an external applied voltage, as in
electrolysis, or if a voltage is created by a chemical reaction, as in a battery,
it is an electrochemical reaction.
• Electrochemistry is important for creating new technologies that are
ecofriendly
• Importance of Electrochemistry
✓ Production of metals like Na, Mg. Ca and Al.
✓ Electroplating.
✓ Purification of metals.
✓ Batteries and cells used in various instruments.

This leads to formation of a layer of negative ions or positive ions around the
metal electrode (Helmholtz electrical double layer),resulting in potential
difference between the metal and the solution.

Measurement of Electrode Potential


• When an electrode is in contact with the solution of its ions in a half-cell,
it has a tendency to lose or gain electrons which is known as electrode
potential. It is expressed in volts. It is an intensive property, i.e.,
independent of the amount of species in the reaction.
• Oxidation potential The tendency to lose electrons in the above case is
known as oxidation potential. Oxidation potential of a half-cell is inversely
proportional to the concentration of ions in the solution.
• Reduction potential The tendency to gain electrons in the above case is
known as reduction potential. According to IUPAC convention, the
reduction potential alone be called as the electrode potential unless it is
specifically mentioned.
• E°red = – E°oxidalion
• It is not possible to determine the absolute value of electrode potential. For
this a reference electrode [NHE or SHE] is required. The electrode
potential is only the difference of potentials between two electrodes that
we can measure by combining them to give a complete cell.
• Reference Electrode
The electrode of known potential is called reference electrode.
It may be primary reference electrode like hydrogen electrode or secondary
reference electrode like calomel electrode.
• Standard Hydrogen Electrode (SHE)
Standard hydrogen electrode (SHE). also known as normal hydrogen electrode
(NHE), consists of platinum wire, carrying platinum foil coated with finely
divided platinum black.
The wire is sealed into a glass tube placed in beaker containing 1 M HCl.
The hydrogen gas at 1 atm pressure is bubbled through the solution at 298K. Half-
cell is, pt H2 (1 atm) H+ (1 M)
• In SHE at the surface of platinum, either of the following reaction can take
place
• 2H+(aq) + 2e– → H2(g) Reduction
• H2(g) → 2H+(aq) + 2e– Oxidation
• The electrode potential of SHE has been fixed as zero at all temperatures.
• Its main drawbacks are
1. It is difficult to maintain 1 atm pressure of H2 gas.
2. It is difficult to maintain H+ ion concentration 1 M.
3. The platinum electrode is easily poisoned by traces of impurities.
Hence, calomel electrodes are conveniently used as reference electrodes, It
consists of mercury in contact with Hg2 Cl2 (calomel) paste in a solution of KCl.
Standard Electrode Potential
• The potential difference developed between metal electrode and solution
of ions of unit molarity (1M) at 1 atm pressure and 25°C (298 K) is called
standard electrode potential.
• It is denoted by E°.
Electrochemical Series
• It is the arrangement of electrodes in the increasing order of their standard
reduction potentials.
• Standard Electrode Potential at 298 K

Cell
• An electrochemical cell is a device capable of either generating electrical
energy from chemical reactions or using electrical energy to cause
chemical reactions.
• Example of an electrochemical cell is a standard 1.5-volt cell which is used
to power many electrical appliances such as TV remotes and clocks.
Types of Electrochemical Cells
The two primary types of electrochemical cells are
1.Galvanic cells (also known as Voltaic cells)
2. Electrolytic cells

Electrochemical Cell
Galvanic Cell
Galvanic cell is a device, in which chemical energy from a spontaneous redox
reaction is changed into electrical energy
Practical application of galvanic cell is known as Daniell cell. It is represented as

By convention cathode is represented on the RHS and anode on the LHS.

Function of Salt Bridge


1. It completes the circuit and allows the flow of current.
2. It maintains the electrical neutrality on both sides.
3. Salt-bridge generally contains solution of strong electrolyte such as KNO3,
KCL etc. KCI is preferred because the transport numbers of K+ and Cl– are
almost same
4. It prevents intermixing of solution as well as ions in the two half cells,
which may lead to precipitation reaction.
Electrochemical cells generally consist of a cathode and an anode. The key
features of the cathode and the anode are tabulated below.
Electromotive Force (emf) of a Cell
It is the difference between the electrode potentials of two half-cells and cause
flow of current from electrode at higher potential to electrode at lower potential.
It is also the measure of free energy change.
Standard emf of a cell,

Nernst equation
Defined as the relationship between cell potential to standard potential and to the
activities of the electrically active (electroactive) species. It relates the effective
concentrations (activities) of the components of a cell reaction to the standard cell
potential.
Nernst Equation for the electrode
Consider a general Electrode reaction:

For this the free energy change (ΔG) can be calculated provided standard free
energy change (ΔGº), Gas constant(R),Temperature (T),activity of product
(aproduct) and activity of reactant (areactant) are known, using
This is Nernst Equation, where E is electrode potential, Eº is standard electrode
potential, F is Faraday constant, T is Temperature and R is Gas constant and a is
activity.

Nernst Equation for a Cell

Application of Nernst equation:


i. It can be used to study the effect of electrolyte concentration on
electrode potential.
ii. It can be used for the calculation of the potential of a cell under non-
standard conditions.
iii. Determination of unknown concentration of one of the ionic species in
a cell is possible, provided Eᵒcell and concentration of other ionic
species is known.
iv. The pH of a solution can be calculated from the measurement of emf
and Nernst equation.
v. It can be used to find the valency of an ion or the number of electron
involved in the electrode reaction.

Battery
A battery is a device in which number of electrochemical cell are connected in a
series. It transformed chemical energy into electrical energy.
Classification of Batteries
i) Primary battery
ii) Secondary battery
iii) Fuel cell
Primary batteries - Primary batteries are those in which only one redox
reaction occurs and battery become dead after some time.
These are non-rechargeable and cell reaction are irreversible.
For example: lithium cell, dry cell, mercury cell
Secondary batteries Secondary batteries are those which recharge when
electric current pass through the cell.
These are rechargeable and cell reactions are reversible, therefore they can be
use again and again.
For example: lead storage battery (lead acid battery), Ni-Cd battery.
Fuel cell Fuel cell is a device, which produce electricity by the combustion of
fuel.
Fuel + oxygen oxidation products + electricity
Lead Storage Battery
Anode: spongy metallic lead
Cathode: Lead dioxide
Electrolyte: dil. H2SO4
Construction:
A number of spongy lead plates (anode) and a number of lead dioxide (PbO 2)
plates (cathode) are connected in parallel. The spongy lead plates are fit
alternatively between lead dioxide plates. All the plates are separated from
adjacent plates by insulators like wood strips, glass fiber etc. The entire
combination is immersed in approximately 38 % dil. H2SO4 of specific gravity
1.2 to 1.3 g/cm3 solution.

Discharging
Battery is said to be discharge when used for production of electrical energy.
In this process the lead electrode loses electron and get oxidized into Pb +2 which
react with 𝑆𝑂4 2− and form PbSO4.
• At anode: Pb Pb+2 + 2e-
Pb+2 + 𝑆𝑂4 2− PbSO4
Net Anode Reaction: Pb + 𝑆𝑂4 2− PbSO4 + 2e-
The released electrons from anode are used up by cathode to reduce PbO2 into
Pb+2 which react with 𝑆𝑂4 2− and form PbSO4.
• At cathode: PbO2 + 4H+ + 2e- Pb+2 + 2H2O
Pb+2 + 𝑆𝑂4 2− PbSO4 ↓
Net Cathode Reaction: PbO2 + 4H+ + 𝑆𝑂4 2− + 2e- PbSO4 ↓ + 2H2O
• The net reactions
Pb + PbO2 + 4H+ + 2 𝑆𝑂4 2− 2 PbSO4 + 2H2O + energy
In this process PbSO4 deposited on both the electrode and cell stop working.
Charging
A battery needs charging when the specific gravity of H2SO4 falls below 1.2
g/cm3 .
This can be achieved by applying external direct current so as to reverse the cell
reaction.
At Cathode:
PbSO4 + 2e- Pb + 𝑆𝑂4 2−
At Anode:
PbSO4 +2H2O PbO2 + 4H+ + 𝑆𝑂4 2− + 2e-
The net reaction
2 PbSO4 + 2H2O + energy PbO2 + 4H+ + 2 𝑆𝑂4 2− + Pb

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