Electrochemistry

Electrochemistry deals with the relationship of chemical reactions

and electricity
Electrochemistry is a branch of chemistry which deals with the
interconversion of chemical and electrical energy.
There are 2 types of devises which allow the conversion of
chemical to electrical energy and vice-versa.
They are galvanic and electrolytic cells
 Electrochemical Cells
Daniell Cell

This cell converts the chemical energy liberated during the redox
reaction to electrical energy with electrical potential equal to 1.1 V.
Such a device is called a galvanic or a voltaic cell
Electrochemical cells containing non spontaneous chemical
reactions are called Electrolytic cells.
Electrochemical cells containing spontaneous chemical reactions
are called Voltaic or Galvanic cells
Functioning of Daniell cell when external voltage opposing the
cell potential is applied.
 Galvanic Cells
Electrochemical cells containing spontaneous chemical reactions are
called Voltaic or Galvanic cells
Redox reaction that occurs is
Zn + Cu2+  Zn2+ + Cu
The anode half reaction: Zn(s)  Zn+2(aq) + 2e-

The cathode half reaction: Cu+2(aq) + 2e-  Cu(s)

The reduction half reaction occurs on the copper electrode while the
oxidation half reaction occurs on the zinc electrode
The part of the Galvanic cell where the Zn metal is oxidized to Zn +2 is
called the anode while the cell where Cu+2 is reduced to Cu metal is
called the cathode.
Each container is called a half-cell and must be separated from each
other to prevent the reaction from taking place without the electrons
flowing through the wire

Filled
with a
gel-like
material
like agar
A potential difference developed between the electrode and the
electrolyte which is called Electrode potential.
When the concentrations of all the species involved in a half-cell is
unity then the electrode potential is known as Standard electrode
potential.
The overall standard potential of a Galvanic cell is equal to the sum
of the standard half-cell reduction-oxidation potentials.
E ocell = E oox + E ored
The potential difference between the two electrodes of a galvanic
cell is called Cell Potential. It is called the cell electromotive force
(emf) of the cell when no current is drawn through the cell.
Example:
Cell reaction: Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s)
Half-cell reactions:
Cathode (reduction): 2Ag+(aq) + 2e–→2Ag(s)
Anode (oxidation): Cu(s) →Cu2+(aq) + 2e–

The cell can be represented as Cu(s)|(aq)|||(aq)|Ag(s)

Ecell= Eoxi– Ered= –
 Nernst Equation
For the electrode reaction:
Mn+(aq) + ne–→M(s)
The electrode potential at any concentration measured with respect to
standard hydrogen electrode is:

but concentration of solid M is taken as unity

R is gas constant (8.314J )

F is Faraday constant (96487 C )
T is temperature in kelvin
[] is the concentration of the species,
 Equilibrium Constant from Nernst Equation
Consider the following cell reaction in equilibrium then
Zn(s) + Cu2+(aq) →Zn2+(aq) + Cu(s)
Then Nernst equation is:

Electrode potential
Reduction half reaction
At equilibrium:
Equilibrium point

Oxidation half reaction

Progress of reaction
Electro-chemical Cell and Gibbs Energy of the Reaction

Electrical work done in one second is equal to electrical potential

multiplied by total charge passed.
The reversible work done by a galvanic cell is equal to decrease in its
Gibbs energy

Eg: Zn(s) + Cu2+(aq) →Zn2+(aq) + Cu(s) ; ∆rG= – 2FE(cell)

If the concentration of all the reacting species is unity, then E (cell) =

E0(cell)
 Conductance of Electrolytic Solutions
The electrical resistance of any object is directly proportional to its
length, l, and inversely proportional to its area of cross section, A.
𝑙 𝜌𝑙
𝑅∝ 𝑅=
𝐴 𝐴

The inverse of resistance, R, is called conductance, G

𝟏 𝑨 𝑨
𝑮= = =κ
𝑹 𝝆𝒍 𝒍
The SI unit of conductance is Siemens(s)
The inverse of resistivity is called conductivity (specific conductance)
is represented by the symbol, κ
The SI units of conductivity are
Electrical conductance through metals is called metallic or electronic
conductance and is due to the movement of electrons.
The electronic conductance depends on:
the nature and structure of the metal
the number of valence electrons per atom
temperature (it decreases with increase of temperature)
Measurement of the Conductivity of Ionic Solutions
Conductivity of ionic solution is determined using a specially designed
vessel called conductivity cell.

Conductivity Cells
Conductivity cell consists of two platinum electrodes coated with
platinum black.
The area of cross section is equal to ‘A’ and distance between
electrodes is ‘’. The resistance of such a column of solution is
𝜌𝑙 𝑙
𝑅= =
𝐴 κ𝐴
The quantity l/A is called cell constant denoted by the symbol, G*.
Once the cell constant and the resistance of the solution in the cell is
determined, the conductivity of the solution is given as:
𝑐𝑒𝑙𝑙 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 G∗
κ= =
𝑅 𝑅

Molar conductivity =
Variation of Conductivity and Molar Conductivity
with Concentration
Conductivity always decreases with decrease in concentration both,
for weak and strong electrolytes.
Molar conductivity increases with decrease in concentration.
When concentration approaches zero, the molar conductivity is
known as limiting molar Conductivity
For strong electrolytes, Λ increases slowly with dilution and is
represented by:
 Kohlrausch law of independent migration of ions
The law states that limiting molar conductivity of an electrolyte can
be represented as the sum of the individual contributions of the anion
and cation of the electrolyte.

are the limiting molar conductivities of the cation and anion

respectively

are limiting molar conductivity of the sodium and chloride ions

respectively, then the limiting molar conductivity for sodium
chloride is
 Electrolytic Cells And Electrolysis
Faraday’s Laws of Electrolysis

First Law:
The amount of chemical reaction which occurs at any electrode during
electrolysis by a current is proportional to the quantity of electricity
passed through the electrolyte
Second Law
The amounts of different substances liberated by the same quantity of
electricity passing through the electrolytic solution are proportional to
their chemical equivalent weights .
 Batteries
A battery is a storage device used for the storage of chemical energy
and for the transformation of chemical energy into electrical energy

Battery consists of group of two or more electric cells connected

together electrically in series.

Batteries are of 3 types. Namely

• Primary Batteries (or) Primary Cells

• Secondary Batteries (or) Secondary Cells

• Fuel Cells (or) Flow Batteries

 Primary Batteries

Primary cells are those cells in which the chemical reaction occurs
only once and the cell becomes dead after sometime and it cannot be
used again.
These batteries are used as source of dc power
Eg: Dry cell (Leclanche Cell)
Mercury cell, lithium cell
 Dry cell:
The electrode reactions are
Zn + 2 MnO2 + 2 NH4+ → Zn+2 + Mn2O3 + 2 NH3 + H2O

At anode : (Oxidation ) Zn(s) → Zn+2(aq)+2e-

At Cathode : (Reduction ) MnO2+ NH4++ e–→ MnO(OH) + NH3

The cell is called dry cell because of the

absence of any liquid phase, even the
electrolyte consists of NH4Cl, ZnCl2 and

MnO2 to which starch is added to make a

thick paste which prevents leakage
Mercury cell:
Mercury cell consists of zinc – mercury amalgam as anode and a paste of
HgO and carbon as the cathode
The electrolyte is a paste of KOH and ZnO

Zn(Hg) + HgO(s) → ZnO(s) + Hg(l)

Anode: Zn(Hg) + 2OH–→ ZnO(s) + H2O + 2e–

Cathode: HgO + H2O + 2e– → Hg(l) + 2OH–

 Secondary Batteries

These cells can be recharged by passing an electric current through

them in the opposite direction and can be used again.
Eg: Lead storage battery

Nickel-Cadmium battery
Secondary cells are widely used in cars, trains, motors, electric clocks,
power stations, laboratories, emergency lights, telephone exchange,
digital cameras, laptops etc.
 Lead storage battery:
The cell reactions when the battery is in use are
Pb(s) + PbO2(s) + 2H2SO4(aq) → 2PbSO4(s) + 2H2O(l)

Anode: Pb(s) + SO42–(aq) → PbSO4(s) + 2e–

Cathode: PbO2(s) + SO42–(aq) + 4H+(aq) + 2e– → PbSO4 (s) + 2H2O(l)

On charging the battery the

reaction is reversed and PbSO4 (s)
on anode and cathode is
converted into Pb and PbO2,
respectively.
 Nickel-Cadmium battery:

It consists of cadmium as the negative

electrode (anode) and acting as a positive
electrode (cathode). Potassium
hydroxide(KOH) is used as an electrolyte

The overall reaction during discharge is

Cd (s) + 2Ni(OH)3(s) → CdO (s) + 2Ni(OH)2(s) + H2O (l)

 Fuel Cells
Galvanic cells that are designed to convert the energy of
combustion of fuels like hydrogen, methane, methanol, etc. directly
into electrical energy are called fuel cells.

One of the most successful fuel cell is H2 –O2 fuel cell.

In the cell, hydrogen and oxygen are bubbled through porous

carbon electrodes into concentrated aqueous sodium hydroxide
solution

The cell consists of two inert porous electrodes made of graphite

impregnated with finely divided ‘Pt’ (or) Ni (or) Pd – Ag alloy and a
solution of 2.5% KOH as electrolyte.
 The electrode reactions are
𝐶𝑎𝑡h𝑜𝑑𝑒 : 𝑂 2 ( g )+2 𝐻 2 𝑂+ 4 𝑒− → 4 𝑂𝐻 −

𝐴𝑛𝑜𝑑𝑒 : 2 𝐻 2+ 4 𝑂𝐻 − → 4 𝐻 2 𝑂 +4 𝑒−

𝑂𝑣𝑒𝑟𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 :2 𝐻 2+𝑂2 → 2 𝐻 2 𝑂

Fuel cells produce electricity

with an efficiency of about 70
% compared to thermal plants
whose efficiency is about 40%.
 Corrosion
Oxidation of metals with oxygen to form a metal oxide is called
corrosion.
In some cases a thin layer of oxide coats the metal surface, preventing
further oxidation (Al2O3)

When iron corrodes, the process is called “rusting”. The iron oxide
(Fe2O3) flakes off, exposing more metal to corrosion.
 The cell reactions are:
Anode: Fe(s)  Fe+2(aq) + 2e- Eo = 0.45V
Cathode: O2(g) + 4H+(aq) + 4e-  2H2O(l) Eo = 1.23V
The overall reaction is:
2Fe(s) + O2(g) + 4H+(aq) → 2Fe2+ (aq) + 2 H2O (l) Eo = 1.67V
The Fe+2(aq) produced is further oxidized by dissolved oxygen:
Fe+2(aq) + O2(g) + 4H+(aq)  4 Fe+3(aq) + 2H2O(l)
Fe+3 then forms an insoluble oxide with water giving the familiar red-
brown colored rust.
Fe+3(aq) + 4H2O(l)  Fe2O3.H2O(s) + 6H+(aq)
Corrosion can be prevented in 3 practical ways:
1. Coating – Painting can form an effective coating on the metal
keeping moisture and oxygen away but loses its effectiveness once
scratched.
2. Galvanization – Plating with metals more active than the metal to
be protected prevents corrosion even when the metal used for
plating is scratched.
3. Cathodic Protection – Protects by forming a galvanic cell where a
more active metal is connected electrically to the metal to be
protected. The ‘sacrificial metal’ is preferentially corroded first.