ELECTRODE POTENTIAL

Electrode potential is the potential difference set up between an

element and a solution of its ions . it is a measure of the tendency to
form ions.
When a metal plate is dipped into a solution containing its ions, some of
the atoms from the metal plate will ionize and go into solution as
positively charged ions, leaving behind their valence electron on the
surface of the plate . At the same time some of the metallic ions in
the solution will take up electrons from the metal plate and deposit
themselves as neutral atoms on the plate leaving behind an excess of
anions in the salt
solution.
Metal(s) Metal ion(aq) + electrons

Thus, if a zinc plate is dipped into a solution of zinc tetraoxosulphate (vi),

some zinc passes into solution as Zn2+ ions and the plate becomes
negatively charged on the surface
Due to accumulation of electrons while the solution becomes
positively charged due to excess zinc ions,Zn2+ . The zinc plate
become negatively charged with respect to the solution.

Zn(s) Zn2+(aq) + 2e- ,

Zn(s)/Zn2+(aq)
Electrode potentials vary from one metal ions /metal system to
another and the value depends on:
i. The concentration of ions in the solution: increasing the
concentration of the metal ion will lower the potential difference
between the electrode and solution because more of the metal
ions will be in solution thereby altering the equilibrium process.
ii. The temperature : it increases the potential difference, since it
will increase the ionisation of metal atoms and thus increases the
potential .
iii. The material used.
The temperature and concentration are therefore standardised by
taking a standard temperature of 250C, and using molar solution
of 1M.
STANDARD ELECTRODE POTENTIAL OF A METAL: is the potential
difference set up between the metal and one –molar solution of
its ions at 298K(250C)
Hydrogen has been chosen as an arbitrary standard, with an
electrode potential value of zero at all temperatures.The standard
electrode potential of a given metal ion is then expressed in terms
of the potential difference which exists between the metallic
electrode and the standard hydrogen electrode.
The electrode potential value is positive if electrons flow from the
hydrogen electrode to the metal electrode and negative if
electrons flow from the metal electrode to the hydrogen
electrode.
STANDARD HYDROGEN ELECTRODE : it consist of hydrogen gas at
298K and one atmospheric pressure, blowing over an inert
platinum electrode , immersed in one-molar solution of
hydrochloric acid .The molecules of the free hydrogen gas
dissociate to form atoms on the surface of the platinum ie.
2H+(aq)/ H2(g) system.
G

MEASURING STANDARD ELECTRODE POTENTIAL

The standard electrode potential of metal ions is
measured by connecting it to the hydrogen half-
cell by SALT BRIDGE and a voltmeter to show the
reading.The potential difference between the
two half cells is known as ELECTROMOTIVE
FORCE or e.m.f of the cell.
D

FUNCTIONS OF SALT BRIDGE

It consist of a strong electrolyte(NaCI, KCI, AgNO 3).It allows the
movement of the ions from one solution to the other
solution without mixing of the two solutions ie helps to
maintain electrical neutrality within the internal circuit by its
ions diffusing into the separate half-cell to balance the
building chargs at the electrodes
 ELECTROMOTIVE FORCE(e.m.f) OF A CELL
It is the maximum potential difference between two electrode of a
cell . When two half –cells are joined together through a salt
bridge, the e.m.f is the algebraic difference between the two
electrode potentials.Hence, the e.m.f of the cell (Eθ total) formed
by the system, Zn(s)/Zn2+(aq)// Cu2+(aq)/ Cu(s) is defined as the standard
electrode potential of the right –hand electrode, ie Cu2+(aq)/ Cu(s)
minus the standard electrode potential of the left hand electrode
ie
Zn(s)/Zn2+(aq)// Cu2+(aq)/ Cu(s)
While // represents the salt bridge
Eθ total= Eθ (RHE) - Eθ (LHE)
Positive e.m.f indicates that the left-hand electrode(zinc) is capable of
reducing copper ions to copper while negative e.m.f indicates that
The left –hand electrode cannot reduce zinc ions to zinc.A positive
e.m.f indicates that the reaction is thermodynamically feasible,
as written down from left to right while a negative e.m.f implies
that the reaction is thermodynamically not feasible as written
down.
CONVENTIONAL WAY OF REPRESENTING CELL DIAGRAM.
The negative electrode is written on the left(oxidation) while the
positive electrode is written on the right(reduction).the double
stroke representing the salt bridge.
For example, to represent half cell of Zn and Cu
Zn(s)/Zn2+(aq)// Cu2+(aq)/ Cu(s)
 Calculation involving e.m.f
Given that: , Zn(s)/Zn2+(aq) ; Eθ =-0.76V
Cu2+(aq)/ Cu(s) ; Eθ =+0.34V.
Calcuate the e.m.f of the Daniel cell
Solution
Eθ = Eθ (RHE) - Eθ (LHE)
+0.34-(-0.76)
= +1.10V
2. Consider the following half-cell reaction
Cu2+(aq) + 2e- Cu(s) ,Eθ =+0.34V
Fe2+ + 2e- Fe(s) ,Eθ =-0.44V
Calculate the e.m.f of the galvanic cell formed by using the Cu 2+/Cu
and Fe2+/Fe couple.
• Solution
• Eθ cell =0.34-(-0.44)
• = 0.34+0.44
• = 0.78V
• 3. Calculate the emf of the cell for the reaction
• Mg(s) + 2Ag+(aq) Mg2+(aq) + 2Ag(s)
• Given;
• Eθ Mg/Mg2+ =-2.3V
• Eθ Ag+/Ag = +0.8O
• Eθ = 0.80-(-2.3)
• = 3.17V
 ELECTROCHEMICAL CELLS
The chemical change which involve the flow of electric current are
called electrochemical changes.
It is broadly grouped into two:
Electrochemical or galvanic cell
Electrolytic cell
ELECTROCHEMICAL CELL: it is a device that convert chemical
energy to electrical energy . In these cells , spontaneous redox
reaction is used to generate an electric current which may be
used for running heater, fan etc.
ELECTROLYTIC CELL: it is a cell in which electrical energy is
converted into chemical energy . In this cells electrical energy is
used to drive reaction and are not spontaneous
Difference between the galvanic cell and
electrolytic cell
Galvanic cell Electrolytic cell
1. It converts chemical energy It convert electrical energy
to electrical energy
2.Anode is negatively charge Cathode is negatively charged
and cathode is positively and anode is positively
charged. charged.
3.It consist of two different half It consist generally of single
cell and a salt bridge compartment
4.Spontaneous redox reaction Non-spontaneous redox
takes place in galvanic cell.it reaction takes place in an
means electron generated from electrolytic cell.it means that
redox reaction electron are generated from
eternal electrical device
The device in which electrical energy is produced from chemical
reactions are called ELECTROCHEMICAL CELL or GALVANIC CELL
or VOLTAIC CELLS.
In these cells, oxidation and reductions reactions occur in
separate containers called HALF CELLS and the redox reaction is
spontaneous(it takes place on its own without external
help).Electrical energy is produced during such reaction.
An example of an electrochemical cell is a zinc electrode dipped
into a zinc tetraoxosulphate(vi) connected to a copper electrode
dipped into a copper(ii) tetraoxosulphate(vi). The two solutions
are separated by a porous partition(salt bridge). The porous
partition allows electrical contact but prevents excessive mixing
of the electrolyte by diffusion . The metallic rods are connected
to the ammeter used to note the passage of current which
moves in opposite direction to the flow of electrons
During the reaction, zinc is oxidised to Zn2+ ions which go into the
solution . Therefore,
Zn(s) Zn2+(aq)+ 2e- (oxidation)
The zinc rod gradually loses its weight. The electrons released at
the zinc electrode move towards the electrode through outer
circuit . Here , these are accepted by Cu2+ ions of CuSO4 solution
which are reduced to copper. The metal gets deposited on the
copper electrode. Cu2+(aq) + 2e- Cu(s) (reduction).the flow
of electron is seen as electric current.
The zinc electrode where electrons are released or oxidation
occurs is called ANODE while the copper electrode where
electrons are accepted or reduction occurs is called CATHODE.
As the electrons move from zinc rod to the copper rod, the zinc
rod is regarded as NEGATIVE TERMINAL while copper rod is
regarded as POSITIVE TERMINAL. There is flow of electrons
from negative terminal (anode) to positive terminal(cathode).
 TYPES OF ELECTROCHEMICAL CELLS
Electrochemical cells are grouped into two: primary cell and
secondary cell.
PRIMARY CELLS: they are cells that are designed to be used once
and discarded . It can not be recharged with electricity . The
electrochemical reaction occuring in the cell is irreversible,
rendering the cell unrechargeable .Examples are cell or
batteries used in appliances such as torches, radios , bicycle
lamps and toy vehicle.
Primary cells are Daniel cell and leclanche-
DANIEL CELL : This type of cell consists of a copper vessel filled
with saturated solution of copper(ii) tetraoxosulphate (vi) and a
porous pot filled with a zinc tetraoxosulphate(vi) solution.
Immersed in the zinc tetraoxosulphate(vi) is a zinc rod.The initial
e.m.f of Daniel cell is about 1.1V.
In Daniel cell, the zinc goes into the solution as
Zn2+ .Zn Zn2+ + 2e-
And the electrodes produced flow in the external circuit to the
copper electrode where Cu2+ ions in solution accept them and
deposit.
Cu2+ + 2e- Cu

For example, the cell diagram for the Daniel cell is represented by
Zn(s)/ Zn2+(aq) // Cu2+(aq)/ Cu(s). The flow of electrons creates an
electrical current that can be used to power electrical devices.
LECLANCHÈ CELL : The cell has a wide range of uses in small electrical
appliance such as torch, radio, electrical bell, clocks etc.It supplies low
current for a short time.
It consists of a zinc metal container as the anode and a graphite rod
surrounded by manganese(iv) oxide as the cathode . The electrolyte is a
paste of the ammonium chloride.
CELL REACTION
AT THE ANODE: The zinc atoms lose two electrons each to dissolve in the
electrolyte as positive charged zinc ions.
Zn Zn2+ + 2e- (oxidation)
The released electrons pass through an external circuit, performing useful
functions of lighting-up of a torch bulb or making a transistor radio work,
before arriving at the cathode.
AT THE CATHODE : Ammonium ion accepts electrons from the graphite rod,
and is reduced to ammonia gas with evolution of hydrogen gas which is
removed by MnO2 acting as depolarizer(gas removers)
2NH +4(aq) + 2e- 2NH3(aq) + H2(g)
 MnO2(g) + H2(g) Mn2O3(s) + H2O(I)
The total cell reaction is,
Zn(s) + NH+4(aq) + 2MnO2(s) Zn2+(aq) + 2NH3(aq) +Mn2O3(aq) + H2O(I)

SECONDARY CELL: it is a electrical cell which can be charged, discharged

into a load and recharged .it supplies higher current.examples of
secondary cells are lithium ion battery, lithium polymer battery, lead acid
battery, Nickel-cadium battery , nickel metal hydride battery. A secondary
cell do not need salt bridge
LEAD ACID BATTERY: it is commonly used as a car battery.The cathode of a
fully-charged accumulator is lead(iv) oxide, PbO2, and its anode is metallic
lead. The electrolyte is dilute tetraoxosulphate(vi) acid solution,H2SO4.
When the two electrodes of a lead accumulator are connected to an
external circuit, it produces electricity by discharging.
AT THE ANODE(DISCHARGING): The lead atom release two electrons each
to become oxidised to lead(ii) ions,Pb2+ ,which then combines with
tetraoxosulphate(vi) ions,SO2-4 in the electrolyte to become deposited
on the anode as lead(ii) tetraoxosulphate(vi),PbSO4
•Pb(s) Pb2+(aq) + 2e-
•Pb2+(aq) + SO42-(aq) PbSO4(aq)
The electrons released pass round an external circuit as an electric current before arriving at the
cathode.
AT THE CATHODE(discharging) : The electrons from the anode are accepted at the cathode where
the lead(iv)oxide and the hydrogen ions from the electrolyte undergo reduction to produce
lead(ii) ions and water. PbO2 + 4H+ + 2e- Pb2+(aq) + 2H2O(I)
The lead(ii) ion combines with the tetraoxosulphate (vi) ion from the electrolytes to become
deposited as lead(ii) tetraoxosulphate (vi).
Pb2+(aq) + SO42-(aq) PbSO4(s)
During the discharging process , the density of the acid decreases to 1.15gcm -3 , due to the
absorption of hydrogen and tetraoxosulphate(vi) ions from the electrolyte; and the e.m.f of the
cell drops to 1.8V.
RECHARGING OF LEAD ACID BATTERY: during the recharging process , the redox reactions at the
respective electrodes in the cell are reversed because it is an electrolysis . the electrode which
anode becomes the cathode and the cathode becomes the anode and the cathode of an external
electrical source are connected to the cathode and anode of the recharging cell respectively.
AT THE CATHODE
•PbSO4(s) Pb2+ + SO42+
•Pb2+ + 2e- Pb(s)
AT THE ANODE:
PbSO4 Pb2+ + SO4
Pb2+ is oxidized to Pb4+ in PbO2
Pb2+ + 2H2O PbO2 + 4H+ + 2e-
H+ combines with SO42- to form the electrolyte,H2SO4.
4H+ + SO42- 2H2SO4
The overall reaction at the anode
PbSO4(s) + 2 H2O(I) PbO2(I) + 4H+(aq) + 2e-
 Corrosion as an electrochemical process
Corrosion of iron is also known as rusting and it is an electrochemical
process.Iron rust when it comes into contact with air and water
because electrochemical cells are set up at the surface of contact.
AT THE ANODE: The center with high concentration of water and low
oxygen serves as the anode. iron is oxidized to give iron(ii) ions,
Fe2+ . Fe Fe2+ + 2e-
AT THE CATHODE: the part of iron at the circumference serves as the
cathode and has high oxygen.the oxygen is reduced by the
electrons from the anode to give hydroxide ions, OH-
2O2(aq) + H2O(I) + 2e 2OH-
1/ -

The iron(ii) and hydroide ions diffuse away from the anodic and
cathodic region and settle down as iron(ii)hydroxide,Fe(OH)2
which is then further oxidised to hydrated iron(iii) oxide which is
rust
• Fe2+(aq) + 2OH-(aq) Fe(OH)2(aq)
• Fe(OH)2(s) + 1/2 O2(aq) Fe2O3.2H2O

• ASSIGNMENT
1.What is the difference between galvanization and tin-plating
2. Explain why tin-plated iron container corrode more than
galvanized iron container.
3. Explain uses of electrolysis.(write it in your note)