Electrochemistry

Electrochemistry is defined as that branch of chemistry

which deals with the study of the production of electricity
from the energy that is released during spontaneous
chemical reactions and the use of electrical energy to bring
about non-spontaneous chemical transformations.
Electrochemical cells

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.
These cells are generally classified into two types.
(a) Electrolytic cells
(b) Voltaic or galvanic cells.
Electrolytic cells
An electrolytic cell can be defined as an electrochemical
device that uses electrical energy to facilitate a non-
spontaneous redox reaction.
Electrolytic cells are electrochemical cells that can be used
for the electrolysis of certain compounds. For example,
water can be subjected to electrolysis (with the help of an
electrolytic cell) to form gaseous oxygen and gaseous
hydrogen.
The three primary components of electrolytic cells are:
Cathode (which is negatively charged for electrolytic cells)
Anode (which is positively charged for electrolytic cells)
Electrolyte
Typical electrolytic cell.
Voltaic or galvanic cell
 An electrochemical cell that converts the chemical energy of
spontaneous redox reactions into electrical energy is known
as a galvanic cell or a voltaic cell. Parts of Galvanic Cell
 Anode – Oxidation occurs at this electrode.
 Cathode – Reduction occurs at this electrode.
 Salt bridge – Contains electrolytes which are required to
complete the circuit in a galvanic cell.
 Half-cells – reduction and oxidation reactions are separated
into compartments.
 External circuit – Conducts the flow of electrons between
electrodes.
 Eg: A Daniell cell
Construction of Daniell cell
A Daniell cell is the best example of a galvanic cell
which converts chemical energy into electrical energy.
It consists of two electrodes of dissimilar metals, Zn
and Cu.
It consists of two half-cells.
 One half-cell is zinc rod dipped in 1M solution of
ZnSO4. The other half-cell is copper rod dipped in a
solution of 1M solution of CuSO4.
A porous partition or a salt bridge separates the two
half-cells from each other. The two electrodes are
connected together externally by a metal wire.
Involved cell reaction is
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
 Cell Reactions and Diagram

In Zn/ZnSO4 half cell,

 oxidation reaction occurs.
Zn → Zn2+ + 2e–
In Cu/CuSO4 half cell,
reduction reaction occurs.
Cu2+ + 2e– → Cu
The net cell reaction is
Zn + Cu2+ ⇌ Zn2+ + Cu
Cell notation:
Zn/Zn2+ || Cu2+/Cu
Cell Notation
Cell notation or cell representation in chemistry is a
shorthand method of expressing a reaction in a
Galvanic cell.
 Salt bridge
It maintains electrical neutrality in two compartments by
allowing movement of anions towards anodic compartments
and cations towards cathodic compartment.
It is a glass tube having potassium chloride or ammonium
nitrate in a gelatin form.
The gelatin allows ionic movement but prevents any kind of
mixing.
In the case of potassium chloride or ammonium nitrate the
ionic mobilities of cations and anions are the same.
Function of salt bridge

A salt bridge acts as an electrical contact between the

two half cells.
It prevents mechanical flow of solution, but it provides
a free path for the migration of ions, to maintain an
electric current through the electrolyte solution. It
prevents the accumulation of charges.
A salt bridge helps in maintaining the charge balance
in the two half cells.
A salt bridge minimizes or eliminates the liquid
junction potential.
Difference between Galvanic and Electrolytic cell
Single electrode potential
Depending upon the tendency of an element or metal to loose
or gain electron, electrode potential may be of two types
namely oxidation potential and reduction potential .
Oxidation potential measures electron loosing capacity and
reduction potential measures the electron gaining capacity of
the electrode system.
Oxidation and reduction potentials are numerically identical
and opposite in sign.
Measurement of electrode potential
 Calomel Electrode
The calomel electrode is widely used as a secondary
reference electrode. It is the mercury-mercurous chloride
electrode. It consists of a glass vessel having a bent side
tube. Pure mercury is placed at the bottom of the tube.
Which is covered with a paste of mercury- mercurous
chloride (Hg+Hg2Cl2) i.e., calomel. The remaining portion
of the cell is filled with a solution of normal (1 N) or
decinormal (0.1 N) or saturated KCl.
A platinum wire sealed into a glass tube is dipped into
mercury layer is used to provide the external electrical
contact. The side tube is used for making electrical contact
with a salt bridge.
When it acts anode, (Oxdn reaction)
2Hg(l) → 2Hg+ + 2e-
2Hg+ + 2Cl- → Hg2Cl2
Overall reaction:
2 Hg + 2Cl- → Hg2Cl2 + 2e-
When it acts as cathode, [Redn reaction]
 2Hg+ + 2e- → 2 Hg
Hg2Cl2 → 2Hg+ + 2Cl-
Overall reaction:
 Hg2Cl2 + 2e- → 2Hg (l) + 2 Cl-
It is easy to set up, compact, small sized and transported easily.
It is a reversible electrode and can be connected to salt bridge
easily. It delivers constant potential throughout the experiment.
Electrochemical Series
A series of electrode materials
formed in order of increasing
standard reduction potential
or decreasing oxidation
potential value is called
electrochemical series.
It is also called activity
series or EMF series.
Application of ECS
1. To Compare Oxidizing and Reducing Strengths
Electrochemical series helps us to identify a good oxidizing
agent or reducing agent. All the substance appearing on the
top of the electrochemical series are a good reducing agent
i.e., they have positive value of standard oxidation potential
whereas those appearing on the bottom of the electrochemical
series are a good oxidizing agent i.e., they have a positive
value of standard reduction potential.
For Example, F2 electrode with the standard reduction
potential value of +2.87 is a strong oxidizing agent and
Li+ with standard reduction potential value of -3.05 volts is a
strong reducing agent.
2. To predict whether a metal can or cannot displace other
metal from its salt solution.
Metals having lower reduction potential can displace those
metals having higher reduction potential from their salt
solution. It means metals lying above in ECS can displace
only those metals from salt solution which lie below in ECS.
For example;
Zn + CuSO4 → ZnSO4 + Cu.
Cu + ZnSO4 → No reaction.
By considering above fact that if copper sulphate solution is
kept in a zinc container, reaction occurs. So, it cannot be
stored. Similarly, if zinc sulphate solution is kept in a copper
container no reaction occurs. So, it can be stored.
3. Calculation of Standard emf (Eo) of Electrochemical Cell
The standard emf of the cell is the sum of the standard
electrode potential of the two half cell: reduction and oxidation
half cell.
Eocell = ( EoCathode ) Reduction + ( EoAnode ) Oxidation
By convention, the standard oxidation potential is always
expressed in terms of reduction potential.
Thus, standard oxidation potential (Eoox) = – standard reduction
potential( Eored . ) Therefore,
Eocell = ( EoCathode ) Reduction - ( EoAnode ) Reduction
Eocell = ( standard reduction potential of reduction half cell) –
(standard reduction potential of oxidation half cell)
Eocell = EoRight – EoLeft
4. Predicting the Feasibility of Redox Reaction
Any redox reaction would occur spontaneously if the free
energy change (ΔG) is negative. The free energy is related to
cell emf in the following manner:
ΔGo = - nFEo
Where n is the number of electrons involved, F is the Faraday
constant and Eo is the cell emf.
ΔGo can be negative if Eo is positive.
When Eo is positive, the cell reaction is spontaneous and serves
as a source of electrical energy.
If it comes out to be negative than the spontaneous reaction
cannot take place.
The resultant value of Eo for redox reaction is important in
predicting the stability of a metal salt solution when stored in
another metal container.
 Commercial Batteries
These are source of electrical energy which may have one or
more cells connected in series. For a good quality battery it
should be reasonably light. compact and its voltage should not
vary appreciably during its use and should have reasonably
long life.
 There are mainly two types of commercial batteries; primary
cells and secondary cells.
Primary battery:
The reaction in a primary battery occurs only once.
The battery becomes dead after used once and cannot be
reused
Example of primary cell is dry cell , mercury cell, fuel cell,
cadmium cell etc.
 Dry cell ( Leclanche cell )
Construction of Dry Cell
a) It consists of a zinc cylinder. This is filled with a moist paste
of NH4Cl and little of ZnCl2.
b) The zinc cylinder acts as a anode. The cathode is a graphite
(carbon) rod.
c) The carbon rod is surrounded by a black paste of manganese
dioxide (MnO2) and carbon powder.
d) During use, the zinc case gets consumed and in the end, it
will develop holes which are responsible for leakages. The
leak proof cells or dry cells have an iron or steel sheet covering
the zinc.
 Working of Dry Cell
 Zinc loses electrons and Zn2+ ions dissolve in the electrolyte. The electrons
pass around the external circuit and are taken up at cathode. This causes
discharge of NH4+ ions from the electrolyte.
 The reactions taking place at the electrodes are:
 Anode: Zn —–> Zn2+ + 2e‾
 Cathode: NH4+(aq) + MnO2(s) +2e¯ ——-> MnO(OH) + NH3
—————————————————————-
Zn + 2NH4+ (aq) + 2MnO2(s) ——->Zn2+ + 2MnO(OH) +2NH3
 In the cathode reaction, manganese is reduced from +4 Oxidation state to
+3 oxidation state. Ammonia is not liberated as a gas but it Combines with
some of the Zn2+ ions produced from the anode to form Complexion
having the formula [Zn(NH3)4]2+
 It gives voltage of approximately 1.2 to 1.5 V. This dry cell does not have
an indefinite life because NH4Cl being acidic corrodes the zinc Container
even when not in use.
  Fuel cell
Fuel cells are primary cells in which reactants are
continuously supplied to the electrodes of the cells from
outside as fuels. Fuel cells use energy of combustion of fuels
like H2, CH4, CH3OH, etc. as the source to produce electrical
energy are called fuel cells.
The fuel cells are pollution free and have high efficiency. One
of the most successful fuel cell uses the reaction of hydrogen
with oxygen to form water.
Hydrogen-Oxygen Fuel Cell
Both electrodes of this cell are made of porous graphite
impregnated with catalyst (Pt, Ag or a metal oxide).
Electrolytic solution of aqueous KOH or NaOH is used.
Oxygen and hydrogen are continuously fed into the cell
through the porous carbon electrode into electrolytic solution.
Involved cell reactions are;
This cell runs continuously as long as reactants are supplied .
Efficiency of such fuel cells is about 60-70% . Research to design
newer fuel cells are being done. Fuel cells are pollution free than
conventional method of method of production of electricity.
Limitations of fuel cells
Though they are pollution free, yet they have some limitations.
Hydrogen is very difficult to store in a vessel. Large amount of are
not readily available hydrogen . Solution to this problem is to
obtain hydrogen by electrolysis of water by using photovoltaic
cells.
  Secondary Cell
Secondary cells can be recharged by passing electricity through
them after every use and cells can be used again and again. In
this, electrical energy is stored in the form of chemical energy
so called storage or accumulator. Such cells are galvanic cells
during discharge and electrolytic cells during recharge.
Examples: lead storage battery, lithium- ion battery etc.
1)Lead accumulators
A lead accumulator is a secondary cell because electrical
energy is not generated within the cell itself but it is
previously stored in it from the external source. It is
reversible cell because cell reactions are reversed if external
e.m.f. just greater than the e.m.f. of this cell is applied. Thus
in this cell, the net cell reaction can be reversed by applying
external opposing e.m.f. greater than the cell e.m.f.
This cell can store electrical energy in form of from
external source (charging) and can supply it during
discharging. The energy is stored in the form of chemical
energy. So this cell is a storage cell or accumulator or
storage battery. Its voltage does not depend on the size of
the electrodes or the size of its cell but depends upon the
strength of a sulphuric acid solution.
A lead accumulator consists of lead plates as the negative
electrode. Lead plates impregnated with lead oxide act as
the positive electrode. Negative and positive electrodes are
arranged in an alternate manner. This assembly of lead
plates is dipped in a non-conducting vessel made up of
glass or plastic or ebonite and containing 38% H2SO4 (sp.
gr. 1.215). All positive plates are connected to each other
and all negative plates are connected to each other.
 Working:
 Discharging of Cell:
 When cell starts working, oxidation takes place at lead plates and
reduction takes place at lead plates with lead oxide. This is called as
discharging of cell.
 2 H2SO4(aq) → 4H+ + 2 SO4 – –
 Reaction at negative electrode (Anode)
 Pb → Pb++ + 2 e–
 Pb++ + SO4– – → PbSO4(s)
 Pb(s) + SO4– – → PbSO4(s) + 2e–
 Reaction at positive electrode (Cathode)
 PbO2(s) + 4H+ + SO4– – + 2e– → PbSO4(s)+ 2H2O(l)
 Net cell reaction during discharging
 Pb(s) + PbO2(s) + 2H2SO4(aq) → 2 PbSO4(s) + 2H2O(l)
 Thus during discharging sulphuric acid is converted into water and hence
specific gravity of sulphuric acid solution falls to 1.17.
 Charging of cell:
 When external e.m.f greater than the e.m.f of this cell is applied, exact
reverse reactions take place. At positive electrode oxidation takes place
and a negative electrode reduction takes place. This is called the
charging of the cell.
 Reaction at negative electrode (Cathode)
 PbSO4(s) + 2e– → Pb(s) + SO4– –
 Reaction at positive electrode (Anode)
 PbSO4(s)+ 2H2O(l) → PbO2(s) + 4H+ + SO4– – + 2e–
 Net Cell Reaction During Charging
 2 PbSO4(s) + 2H2O(l)
 Pb(s) + PbO2(s) + 2 H2SO4(aq)
 Pb(s) + PbO2(s) + 2H2SO4(aq) → 2 PbSO4(s) + 2H2O(l)
 E.M.F. of Cell:
 A fully charged accumulator with 38% H 2SO4 has a voltage about 2.041
V i.e. approx 2 V.
Uses of Lead Accumulator:
Lead accumulators are used in motor cars and other
automotive vehicles and therefore popularly known as car
batteries. Here generally six cells are connected in series to
give a voltage of 12 V.
They are used in laboratories as a source of constant DC
voltage.
They are used in telephone and telegraph offices.
They are used in electric clocks, radio sets, burglar’s alarms
etc.
They are also used as a source of electricity in the initial stages
of the rocket.
2)Lithium –Ion battery:
Lithium ion batteries are rechargeable batteries and cells that
provide improved levels of capacity combined with reliable
As a result of their characteristics, Lithium Ion, or Li-ion
batteries have become the battery technology of choice in a
variety of areas. Li-ion batteries are used almost exclusively in
mobile phones, laptops, e-readers digital camera, flash light,
medical equipment and many other electronic gadgets.
In addition to this, Li-ion technology is also used being used
batteries for power tools, electric vehicle batteries, , electric
inverters, aerospace military and many more applications.
With the increasing reliance on mobile and portable power, the
use of Li-ion battery technology is set to increase still further.
It is worth noting that lithium ion cells and batteries
rechargeable and they are different to lithium batteries or cells
that are primary cells and not rechargeable.
Lithium –ion battery generate the cell potential of 3.6-3.8 V.
A lithium ion battery, or cell of whatever form has four main
constituents:
Cathode: This is the positive electrode and it is typically made
from a lithium based metal oxide like cobalt oxide. There are
several different lithium ion battery technologies, so the exact
format will change from one type to the next.
Anode: This is the negative electrode of the lithium ion battery
and it is generally made from carbon, normally in the form of
graphite.
Electrolyte: The electrolyte is the located between the two
electrodes within the cell. It is often a mixture of organic
carbonates such as ethylene carbonate, diethyl carbonate, etc.
Separator: In order to prevent the two electrodes touching a
separator is placed between the anode and cathode. This absorbs
the electrolyte, and enables the passage of ions, but prevents the
direct contact of the two electrodes within the lithium in cell.
Cell reaction
Reduction takes place at the cathode. There, cobalt oxide
combines with lithium ions to form lithium-cobalt oxide (LiCoO 2).
The half-reaction is:
CoO2 + Li+ + e- → LiCoO2
Oxidation takes place at the anode. There, the graphite
intercalation compound LiC6 forms graphite (C6) and lithium ions.
The half-reaction is:
LiC6 → C6 + Li+ + e-
The overall reaction is;
 (left to right = discharging and right to left = charging):
LiC6 + CoO2 ⇄ C6 + LiCoO2
Lithium-ion Batteries are eco-friendly, lightweight and
compact, have high energy density, low maintenance cost and
low self-discharge rate.