Electrochemistry
Jk Tushit Vijay
XII-B
What is Electrochemistry
It is the study of production of electricity from energy released
during spontaneous chemical reactions and the use of electrical
energy to carry out non spontaneous chemical reactions.
Galvanic cells
Electrochemical cell that converts chemical elegy of a spontaneous
redox reaction to electrical energy , is known as Galvanic cell/Voltaic
cell. e.g. Daniell cell
In this cell, the electrode is dipped in its own salt. This combination
is known as half cell or redox couple.
In a half cell, either reduction or oxidation occurs.
Oxidation: Anode
Reduction:Cathode
The positive sign indicates the electrodes at which electrons enter
the cell .
The negative sign indicates the electrodes at which electrons leave
the cell.
Salt bridge
It is a U shaped type containing electrolytes to be mixed with some
gel.
It plays an important role as it completes the circuit, and it maintains
electrical neutrality of the solutions in their respective half cell.
Important terms related to Cell:
Electrode potential: Potential difference developed
b/w electrode and electrolyte in an electrochemical
cell.
Cell potential: Potential difference between two half
cell is known as cell potential.
Standard electrode potential
Measurement of electrode potential
To measure the half cell
potential, one half cell is
assigned a potential value of
zero, known as Standard
Hydrogen Electrodes.
SHE is represented by
Pt|H2|H+
The electrode has zero potential
at all temperature.
Electrochemical Series
The arrangement of various standard half cells in
order of decreasing values of SRPs is known as
electrochemical series/activity series/electromotive
series.
+E: Redox couple is weak reducing agent.
-E: Redox couple is a strong reducing agent
Nernst Equation
It gives the between the relation between electrode potential,
temperature and concentration of metal ions, is known as
Nernst equation.
1.Nernst equation for electrode potential:
2. Equilibrum Constant for Nernst equation:
Electrochemical cell and Gibbs energy of the reaction:
Conductance of electrolytic solutions
(I) Electronic Conductance /Metallic Counductance
Electronic conductance through the metals is due movement of electrons and it
termed as electronic/metallic conductance.
(II) Electrolytic Conductance/Ionic Conductance
The conductance of electricity of the ions that are present in the solution is
known as electrolytic or ionic conductance.
Measurement of conductivity of ionic solutions.
Accurate measument of unknown resistance iwas performed using Wheatstone
Bridge. We face two problems.
1. Passing DC charges composition of the solution.
2. Solution cannot be directly connected to the bridge.
1. The first difficulty is resolved using AC.
2. The second difficulty is resolved using a specially designed vessel known
as conductivity cell.
Measurement of Cell constant.
For measuring cell constant, the resistance of the cell is
determined by using KCl solution, whose conductivity at
different temperatures and concentration is already known.
Thus, the resistance/conductivity of an electrolyte can be
measured using cell constant, known as Wheatstone Bridge.
The condictivity of the given cell is given by
k = Cell constant/R = G*/R
Molar Conductivity
The condicting power of the ions by dissolving one
gram mole of an electrolyte placed between two
electrodes, with an area A and length l.
/\ = k/C
/\=G/RC
/\=k*1000/M
Strong electrolytes(Debye-Huckel-
Onsager Equation)
For strong electrolytes, /\ has to iincrease slowly with dilution.
It can be represented by Debye-Huckel-Onsager Equation.
Weak Electrolytes:
They do not ionise completely in aqueous as well as molten state is known as weak
electrolyte. Eg: H2CO3, CH3COOH
Kohlrausch Law of Independent Migration Of
Ions
It states that the limiting molar condictivity of an electrolyte, is the sum of
individual contributions of cations and anions of the electrolyte.
/\=/\Na+ = /\Cl-
If the electrolyte produces V+ cation and V- anions, then,
/\=V+/\ + V-/\-
Applications:
1. It determines the /\ of weak electrolyte.
2. In determination of degree of dissociation and equilibrum constant of weak
electrolye.
Faraday’s Laws Of Electrolysis
1.Faraday’s First Law: The amount of chemical reaction
occcuring at any electrode during electrolysisby passing
current is directly proportional to the quantity of
electricity passed to the electrolyte.
W=ZIt
2. Faraday’s Second Law: When the same quantity of
electricity is passed through different electrolyte connected
in series, the weight of different substance liberated at
electrodes is directly proportional to equivalent weight.
W1 /E1 =W2/E2
BATTERIES
It can be divided into the folowing types:
1.Primary Battery
2.Secondary Battery
1.Primary Battery
A primary battery(non rehargable) is a device in which reaction occur once and after
use, the device becomes dead, and it cannot be used again.
The primary battery can be divided into two types: The Dry Cell and Mercury Cell.
Dry Cell
Anode: Zinc metal container.
Cathode: Carbon rod, surrounded by powdered MnO2
and carbon black.
Electrolyte: Moist paste of ammonium chloride and
zinc chloride.
Reactions occuring:
1. At anode: Zn=Zn+2+2e-
2. At cathode: MnO2+NH4+2e-=MnO{OH}+NH3
It is commonly used in transitors and clocks.
Mercury Cell:
Anode – Zinc amalgam.
Cathode – A paste of HgO and carbon.
Electrolyte - A paste of KOH and ZnO
Anode – Zn(Hg) + 2OH- —› ZnO + H2O +
2e-
Cathode – HgO + H2O + 2e- —› Hg + 2OH-
Overall reaction – Zn + HgO —› ZnO + Hg
The cell has a constant potential of 1.35
V, since the overall reaction does not
involve any ion in solution
2. Secondary Batteries
1. A secondary cell after use can be recharged by passing current through it in the
opposite direction.
2. Thus it can be reused again and again
3. Eg;- Lead storage battery
1.Lead Storage Battery
Lead plates acts as anode
Grid of lead plates coated with lead dioxide (PbO2)
acts as a cathode.
A solution of H2SO4 acts as an electrolyte.
Anode: Pb+SO42-=PbSO4+2e-
Cathode: Pb+PbO2+2H2SO4=2PbSO4+2H20
On recharging, cell reaction is reversed.
Nickel Cadmium Battery
Cadmium metal act as anode.
Metal grid containing Nickel(IV)oxide act as
cathode.
KOH solution act as electrolyte.
Cell reaction –Cd(S) + 2Ni(OH)3(s) —›CdO(S) +
2Ni(OH)2(s)+ H2O
Cell reaction is reversed on recharging.
emf is approximately 1.4 V .
Also called Nicad cell.
Fuel Cells
These are galvanic cells which convert the energy
of combustion of fuels like hydrogen,
methane,methanol, etc. directly into electrical
energy.
Eg:- H2 – O2 fuel cell.
Here hydrogen and oxygen are bubbled through
porous carbon electrodes into concentrated
aqueous sodium hydroxide solution.
To increase the rate of electrode reactions,
catalysts like finely divided platinum or palladium
metal are filled into the electrodes.
Corrosion
It is the slow destruction of a metal due to attack of atmospheric gases and
moisture on their surface resulting in the formation of compounds such as
oxide ,sulphide ,carbonate etc.. More reactive metals corrode more easily.
1. Eg: Rusting of iron.
2. Tarnishing of silver,
3. Formation of green coating on copper (verdigris)
Mechanism of Rusting
At a particular spot of the metal, oxidation takes place and that spot behaves as
anode. Here Fe is oxidized to Fe 2+
2Fe(s) —› 2Fe2+ + 4e- (Anode)
Electrons released at anodic spot move through the metal and go to another spot
on the metal and reduce oxygen in presence of H + . This spot behaves as
cathode. [H+ available from H2CO3 or from H2O]
2Fe(s) —› 2Fe2+ (aq)+ 4e- (Anode)
O2 (g)+ 4H+ (aq) + 4e- —› 2 H2O(l) (Cathode)
2Fe(s) + O2 (g)+ 4H+ (aq) —› 2Fe2+ (aq)+ 2 H2O (l) The ferrous ions(Fe2+) are
further oxidised by atmospheric oxygen to ferric ions(Fe3+) which come out
as rust in the form of hydrated ferric oxide, Fe2O3 .x H2O and with further
production of hydrogen ions
Prevention Of Corrosion:
Barrier protection –
By coating with a suitable material –paint,grease
Sacrificial protection –
Coating with a more reactive metal. The process of coating the surface of iron with
Zinc is called Galvanization.
Cathodic protection - Here metal to be protected is set as cathode by attaching
more reactive metal to it.
More reactive metal act as anode.
Now the more reactive metal undergo oxidation.
Antirust solutions – Alkaline phosphate or chromate solutions are applied on iron
surface to form a iron phosphate or chromate coating which prevent corrosion.
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