BATTERIES: THE ELECTROCHEMICAL CELLS

Electrochemical cell is a device that converts chemical energy to electrical energy. A simple
electrochemical cell can be used to prove that electron transfer occurs in a redox reaction. An
electrochemical cell is also known as galvanic cell.
SOME PARAMETERS ASSOCIATED WITH ELECTROCHEMICAL CELL
1. Standard hydrogen electrode: The standard hydrogen electrode consists of hydrogen
gas at 25oC and one atmospheric pressure bubbling around an inert platinum electrode in
contact with one-molar solution of hydrogen ions. It is the reference standard by which the
standard electrode potential of all metal ions/metal system is measured against. The
standard hydrogen electrode potential has been assigned a value of zero volts.
2. Standard electrode potential (Eo): This the tendency of an element to form ions in
solution relative to the tendency of hydrogen atoms to form ions in solution at standard
conditions of 298K of temperature, 1atm of pressure and 1molar concentration. That is, it is
the potential difference set up between the metal and one-molar solution of its ions at 25 oC
arbitrarily taking the standard electrode potential of hydrogen ions/hydrogen gas system as
zero volts.
Factors affecting the values of electrode potentials are:
(i) Concentration of the ions,
(ii) Temperature of the solution
(iii) Pressure of gases involved
The values of standard electrode potentials are used to:
(i) Predict the direction or feasibility of a chemical reaction
(ii) To calculate the e.m.f of a cell
(iii) To predict the standard electrode potential of unknown elements
3. The Salt bridge: It is a piece of filter paper soaked in potassium chloride solution or
ammonium chloride solution. Its functions are to complete the electric circuit and enable the
movement of ions from one half-cell to another so as to maintain electrical neutrality in the
solution.
The following are the importance of a salt bridge in an electrochemical cell
(i) It allow movement of ions between the two components
(ii) It helps to connect both half cells and complete the circuit
Another component that can be used in the place of salt bridge is a porous partition. These
both allow the movement of ions without extensive mixing of the solution. Thus, while
electrons passes through the wire, ions moves through the salt bridge or a porous partition
from one compartment to another.
4. Electrodes: These are conductors in form of wires or rod or plate through which electrons
enters and leave the solution. The reaction in an electrochemical cell occurs at the interface
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between the electrode and the solution where the electron transfer occurs. The electrode
compartment in which oxidation occurs is called the anode; the electrode compartment in
which reduction occurs is called the cathode.
An electrochemical process involves electron transfer at the interface between
electrode and the solution. The reducing agent supplies electrons to the anode
while the oxidizing agent accept electrons at the cathode. In an electrochemical cell,
the anode is the negative electrode while cathode is the positive electrode in an
electrochemical cell.

MEASUREMENT OF STANDARD ELECTRODE POTENTIAL

In measuring the standard electrode potential of particular metal ion/metal system, the half-
2+¿¿
cell of the metal ions/metal system e.g Zn(aq) /Zn(s) is connected to that of hydrogen
ions/hydrogen gas system by a salt bridge at standard conditions of 298K, 1M
concentration and 1atm of pressure. The reading shown on the voltmeter is the
electromotive force or the e.m.f of the cell. Since the standard electrode potential of
hydrogen ions/hydrogen gas system is assigned the value zero, the value obtained is the
standard electrode potential of the metal ion/metal system. The e.m.f of a cell can be
measured using a potentiometer or digital voltmeter.
The sign of the standard electrode potential of a given metal system is dependent on
the direction of the electron flow in the cell. If electron flows from hydrogen ions /hydrogen
gas system to the metal ions/metal system, the standard electrode potential of that metal
system is assigned a positive value. If the flow of electron is in the reverse direction, it is
assigned a negative value.
For example, the standard electrode potential of zinc ions/zinc metal system is -0.76V
because during the measurement, the flow electrons is from zinc system to hydrogen
system. When two half – cells with different electrode potentials are connected through a
salt-bridge, they form a cell called Electrochemical cell. The electrochemical cell is also
called a Galvanic cell.
In the electrochemical cell oxidation occurs in the anode compartment while reduction occurs
in the cathode compartment. The overall redox reaction results in flow of electrons or electric
current.

What Happens in an Electrochemical Cell

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 Consider these half cells: Eo Zn2+/Zn(s) = -0.76V Eo
Cu2+(aq)/Cu(s) = +0.34V

For example, if the Zn2+(aq)/Zn(s) half –cell is connected to Cu 2+(aq) / Cu(s) half cell through a
salt bridge with the Cu2+(aq) /Cu(s) made the right hand electrode, the cell produced is called a
Daniel cell.
In this cell, oxidation occurs at the zinc electrode, this electrode is the negative electrode or
the anode. Reduction occurs at the copper electrode which functions as the positive
electrode or cathode as shown above. The diagram is written in a short – hand form as
Zn(s)/ Zn2+(aq) // Cu2+(aq)/ Cu(s).
An electric current flows through the wire connecting the two metals outside the solution. In
this system, chemical energy is converted to electrical energy. Zinc atoms at the zinc
electrode lose two electrons each (oxidation) to form zinc ions which go into solution. In doing
so, the zinc electrode becomes negatively charged and hence behaves as a negative
electrode or anode. The excess electrons on the zinc electrode move along the wire to the
electron deficient copper (II) ions.
The copper (II) ions thus becomes reduced by gaining two electrons each to form
metallic copper, which deposits itself on the copper electrode. The copper electrode becomes
positively charged and behaves as positive electrode or cathode.

Comparing Electrochemical and Electrolytic cell

It is important to distinguish between the electrochemical cells and electrolytic cell. In both,
oxidation always occurs at the anode and reduction at the cathode.
In an electrochemical cell, the negative electrode is the anode while the positive
electrode is the cathode. In electrolytic cell on the other hand, the negative electrode is the
cathode while the positive electrode is the anode.

CELL NOTATION (LINE NOTATION)

In this notation the anode components are listed on the left and the cathode components are
listed on the right separated by double vertical lines (indicating the salt bridge or porous

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disk). In the anode compartment, the anode material is stated at the far left, while in the
cathode compartment, the cathode material is stated at the far right.
For example in the equation, Zn(s) + Cu2+ Zn2+ + Cu(s)

Zn(s) →
Zn2+(aq) + 2e- oxidation reaction (Anodic reaction)

Cu2+(aq) + 2e- →
Cu(s) reduction reaction (Cathodic reaction)

The line notation will be represented as Zn(s)/ Zn2+(aq) // Cu2+(aq) / Cu(s)..

The single line represent the phase boundary between the metal ions (solution) and the
metal (electrode)
The double lines represent the salt bridge.

In cases, where all the components involved in the oxidation–reduction reaction are ions,
none of the dissolved ions can serve as an
electrode. Therefore, a non-reacting (inert) conductor must be used. The usual choice is
platinum.
Thus, for a cell described as Cu2+ + Fe2+  Cu(s) + Fe3+
The half equations will be
Fe2+  Fe3+ + e- oxidation (anodic) equation
2+ -
Cu (aq) + 2e  Cu(s) reduction (cathodic) equation
Therefore, the cell notation will be
Pt(s)/ Fe2+(aq), Fe3+(aq) // Cu2+(aq)/Cu(s)

Exercise 7:
Write the cell notation for the following reaction
(a) Ag+(aq) + Cu(s)  Ag(s) + Cu2+(aq) (b) Fe(s) + Cu2+(aq)  Fe2+(aq) + Cu(s) (c) Al3+
2+
(aq) + Mg(S)  Al(s) + Mg (aq)
2+ + 3+
(d) Fe (aq) + Ag  Fe (aq) + Ag(s) (e) 2H+(aq) + Zn(s)  Zn2+(aq) + H2(g) (f) 2MnO4-(aq) +
2+ 2+
5Fe(s)  5Fe (aq) + 2Mn (aq) + 8H2O(l)
(g) 2MnO4-(aq) + 6H+(aq) + 5ClO3-(aq)  2Mn2+(aq) + 3H2O(l) + 5ClO4-(aq) (h) What is the
meaning of the single and double line in the cell notation?

Exercise 8:
Write balanced equations for the following cell notations
(a) Mg(s)/Mg2+(aq)//Fe2+(aq)/Fe(s) (b) Sn(s)/Sn2+(aq)//Pb2+(aq)/Pb(s)
2+ 2+
(c) Fe(s)/Fe (aq)//Cu (aq)/Cu(s) (d) Pt/H2(g), H2+(aq)//Cu2+(aq)/Cu(s)
(e) Zn(s)/Zn(aq)//H2+(aq), H2(g)/Pt(s) (f) Zn(s)/Zn2+(aq)//Pb4+(aq), Pb2+(aq)/Pt(s)
2+ - 2- 3+
(g) Pt(s)/Mn (aq), MnO4 (aq)// Cr2O7 (aq), Cr (aq)/Pt(S) (h) Pt(aq)/ClO3- (aq), ClO4-(aq)//Cr2O72-
3+
(aq),Cr (aq)/Pt(s)

THE ELECTROMOTIVE FORCE (E.M.F)

The e.m.f of an electrochemical cell is the algebraic difference between the standard
electrode potentials of the two metallic electrodes
i.e e.m.f = Eocathode – Eo anode. A big e.m.f means a powerful cell. A galvanic cell
consists of an oxidizing agent in one compartment that pulls electrons through a wire from a
reducing agent in the other compartment. The “pull,” or driving force, on the electrons is
called the cell potential or the electromotive force (e.m.f) of the cell.

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If we need a powerful cell the metals which serve as electrode should have very wide
difference in electrode potential. The sign of e.m.f tells whether the reaction is spontaneous
or not. A positive e.m.f shows that the reaction in the cell is spontaneous and so such cell can
work. A negative e.m.f indicates a non-workable (non-spontaneous) cell.

The scientific community has universally accepted the half-reaction potentials based on the
assignment of zero volts to the standard hydrogen electrodes, 2H+(aq) + 2e-  H2(g) (under
standard conditions where ideal behavior is assumed). However, before we can use these
values to calculate cell potentials, we need to understand several essential characteristics of
half-cell potentials.
The accepted convention is to give the potentials of half-reactions as reduction processes. For
example:
2H+(aq) + 2e-  H2(g) E0 = 0.00V
2+ -
Cu (aq) + 2e  Cu(s) E0 = +0.34V
2+ -
Zn (aq) + 2e  Zn(s) E0 = -0.76V

The E0 values corresponding to reduction half-reactions with all solutes at 1M and all gases at
1 atm are called standard reduction potentials. Combining two half-reactions to obtain a
balanced oxidation–reduction reaction often requires two manipulations:

1. One of the reduction half-reactions must be reversed (since redox reactions must involve a
substance being oxidized and a substance being reduced). The half-reaction with the
largest positive potential will run as written (as a reduction), and the other half-reaction
will be forced to run in reverse (will be the oxidation reaction). The net potential of the cell
will be the difference between the two. Since the reduction process occurs at the cathode
and the oxidation process occurs at the anode, we can write E0cell = E0(cathode) – E0 (anode)
2. Since the number of electrons lost must equal the number gained, the half-reactions must
be multiplied by integers as necessary to achieve the balanced equation. However the
value of E0 is not changed when a half-reaction is multiplied by an integer. Since a
standard reduction potential is an intensive property (it does not depend on how many
times the reaction occurs), the potential is not multiplied by the integer required to
balance the cell reaction.

CALCULATIONS INVOLVING E.M.F

The formula for calculate e.m.f. of a cell is given as;
E0cell = E0 (cathode) – E0 (anode)
In a cell notation, it is also given as;
E0cell = E0 (right) – E0 (left)

Example
Find the e.m.f of the cell represented by the half-cell below:
Eo Cu2+(aq)/ Cu(s) = +0.34V and EoAg+(aq)/Ag(s) = +0.80V
Solution:
e.m.f => E0cell= Eo (cathode) – Eo (anode)
= (+0.80) – (+ 0.34)
= +0.46V

RELATIONSHIP BETWEEN E.M.F AND △G

△G is known as the free energy change. The free energy of a system is the energy available
for doing work. A negative value of △G indicate that the reaction is spontaneous. A positive
△G shows that the cell is not spontaneous. The formula for determining the free energy
change of an electrochemical cell is given as

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△G = -nFE
Where;
n= number of moles of electron transfer,
F = Faraday constant (96500c)
E= e.m.f. of the cell

Find the e.m.f and △G of the cell represented by the half-cell below:
Example

Eo Cu/Cu2+(aq)= +0.34v and EoAg+(aq)/Ag(s) = +0.80v

Solution:
e.m.f =>
E0cell= Eo (cathode) – Eo (anode)
= (+0.80) – (+ 0.34)

= +0.46V
△G = -nFE
= 2 x 96500 x 0.46
= -88780J

Exercise 9:

the e.m.f and △G of the cells in each case.

Draw and label the diagram of the electrochemical cells made up of the following. Calculate

(a) Cu2+(aq)/Cu(s); E0 = +0.34V Zn2+(aq)/Zn(s); E0 = -0.76V

(b) Fe (aq)  Fe (aq) E = - 0.77V
3+ 2+ 0
Cu (aq)  Cu(s);
2+
E0= +0.34V
+ 0 2+ 0
(c) Na (aq)/Na(s); E = -2.71V Fe (aq)/Fe(s); E = -0.44V
(d) Ag+(aq) + e-  Ag(s) E0 = +0.80V Cu2+(aq) + 2e-  Cu(s) E0 = +0.34V
(e) Sn2+(aq)/Sn(s); E0 = -0.14V Mn2+(aq)/Mn(s); E0 = -1.18V
(f) Pb2+(aq) + 2e-  Pb(s) E0 = -0.13V Au3+(aq) + 3e-  Au(s) E0= +1.50V
2+ 0
(g) Ca /Ca(s) E = -2.76V Cu (aq)/Cu(s) E0 = +0.34V
2+

(h) Ag (aq) + e  Ag(s) E = +0.80V Fe3+(aq)  Fe2+(aq) E0= - 0.77V

+ - 0

(i) Mn2+(aq)/Mn(s); E0 = -1.18V Cu2+(aq)/Cu(s) E0 = +0.34V

(j) Pb (aq) + 2e  Pb(s) E = -0.13V
2+ - 0
Fe3+(aq)  Fe2+(aq) E0= - 0.77V

Complete Description of an Electrochemical Cell

A complete description of a galvanic cell usually includes four items
a) The cell potential (e.m.f) of the cell and the balanced cell reaction
b) The direction of electron flow (obtained by inspecting the half reactions or by using
directions that gives a positive E0Cell
c) Designation of the anode and cathode
d) The nature of each electrode and the ions present in each compartment.

Example
Describe completely the electrochemical cell based on the following half reactions under
standard condition
Zn2+(aq) + 2e-  Zn(s) E0 = -0.76V (i)
Cu (aq) + 2e  Cu(s)
2+ -
E0 = +0.34V (ii)

Solution
Item 1: Determine the E0cell and the balanced cell reaction
(Note: The electrode with less positive E0 value will serve as the anode, while the electrode
with more positive value serves as the cathode)
E0cell = E(cathode) – E(anode)
E0cell = (+0.34) – (-0.76)

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 E0cell = +1.10V

In determining the balanced cell equation, the half equation for the compartment with the
less positive E0 value (anode) will be reversed
Zn2+(aq)  Zn(s) + 2e-
Cu2+(aq) + 2e-  Cu(s)
Balanced cell Equation:
Cu2+(aq) + Zn(s)  Cu(s) + Zn2+(aq) E0cell = +1.10v

Item 2: Direction of electron flow

(Note: Electrons will flow from compartment with a less positive value to a more positive
value)
Electrons will flow from the compartment containing Zinc to the compartment containing
Cu2+.

Item 3: Designation of anode and cathode

Oxidation occurs in the compartment containing Zn. Thus this compartment function as the
anode.
Reduction occurs in the compartment containing Cu 2+. This compartment functions as
cathode.

Item 4: The nature of each electrode

The electrode in the Cu/Cu 2+ compartment is the Copper metal. The electrode in the Zn/Zn 2+
is the Zinc metal.
(Note: if no metal is present in the compartment, an inert conductor such as platinum must
be used)
The diagram and the line notation for the cell is

E0cell = +1.10v

Exercise 9:
Describe completely the galvanic cell based on the following half reaction under standard
condition
(a) Fe3+(aq)  Fe2+(aq) E0= - 0.77V Cu2+(aq)  Cu(s);
0
E = +0.34V
(b) Ag (aq) + e-  Ag(s)
+
E0 = +0.80V Cu2+(aq) + 2e-  Cu(s)
0
E = +0.34V
(c) Fe2+(aq) + 2e-  Fe(s) E0 = -0.44V MnO4-(aq) + 5e- + 8H+  Mn2++ 4H2O
0
E = 1.51V
(d) Pb2+(aq) + 2e-  Pb(s) E0 = -0.13V Au3+(aq) + 3e-  Au(s)
E0= +1.50V
(e) Ag (aq) + e-  Ag(s)
+
E0 = +0.80V Fe3+(aq)  Fe2+(aq)
0
E = - 0.77V
(f) Pb2+(aq) + 2e-  Pb(s) E0 = -0.13V Fe3+(aq)  Fe2+(aq)
0
E = - 0.77V

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 DEPENDENCE OF CELL POTENTIAL ON CONCENTRATION
The cell potential discussed earlier have been done under standard conditions, where
concentration is 1.0M. It is also possible to determine the cell potential under conditions that
are not standard. For example, under standard conditions, the cell with the reaction Cu (s) +
2ce4+(aq)  Cu2+(aq) + 2Ce3+(aq)  Cu2+(aq) + 2Ce3+(aq) has a potential of 1.36V. What will be cell
potential if [Ce4+] is greater than 1.0M. This question can be answered quantitatively in terms
of Le’ Chateliers principle. An increase in the concentration of Ce 4+ favour the forward
reactions and thus increase the driving force of the electrons. The cell potential will increase.
On the other hand, an increase in the concentration of the product (Ce 3+ or Cu2+) will oppose
the forward reaction and thus decrease the cell potential.

Quiz
For the cell reaction
2Al(s) + 3Mn2+(aq)  2Al3+(aq) + 3Mn(s) E0cell = 0.48V
Predict whether the ECell is larger or smaller than E0cell for the following cases
a. [Al3+] = 2.0M, [Mn2+] = 1.0M
b. [Al3+] = 1.0M, [Mn2+] = 3.0M

NON-STANDARD STATE CONCENTRATIONS

With use, the e.m.f of an electrochemical cell begin to decrease due to changes in the
concentration of the electrolytes. A German scientist Walther Herman Nernst (1864-1941),
gave a mathematical relationship that can be used to predict the e.m.f of a cell at
concentration that is not in a standard state. (1.0M). This equation is known as Nernst
Equation.
The Nernst equation give the relationship between the e.m.f at standard conditions (E 0cell) and
the e.m.f of a cell at any other concentrations (E Cell)
Generally, for a redox equation of the form, aA (aq) + bB(aq) <==> cC(aq) + dD(aq). The Ecell of the
battery at any concentration is given as
C d
0.059 [C ] [d ]
Ecell =¿ E0cell − log a b
n [ A] [B]
Where n= number of electron transferred.
C d
[C ] [d ]
The equation can also be simplified by writing K eq instead of a b to give
[ A ] [B]
0.059
Ecell =¿ E0cell − log K eq
n

Where K eq = equilibrium constant.

Example
Calculate the cell e.m.f of Zn(s)/Zn2+(aq) (0.001M)//Cu2+(aq)(0.100M)/Cu(s) at 250c
E0 Zn2+(aq)/Zn(s) = -0.76V, E0 Cu2+(aq)/Cu(s) = +0.34V
Solution
Since the concentration of the electrolytes are not 1.0M, hence the e.m.f required is a non-
standard state cell potential. This is calculated using Nernst equation:

0.059
Ecell =¿ E0cell − log K eq
n

Anode reaction: Zn(s)  Zn2+ + 2e- E0 = +0.76V

2+ -
Cathode reaction: Cu + 2e  Cu(s) E0 = +0.34
2+ 2+
Overall reaction: Zn(s) + Cu (aq)  Zn (aq) + Cu(s) E0 = +1.10V

E0Cell = +1.10V, n=2, K eq =¿ ¿ ¿ ¿

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 0 0.059
Thus, Ecell =¿ Ecell − log ¿ ¿ ¿ ¿ ¿
n
0.059 [0.001¿¿❑]❑
Thus, Ecell =¿ +1.10− log ¿¿
2 ¿¿¿
= +1.10 – 0.03log(10-2)
= +1.16V

Exercise 9c:
1. Calculate the cell e.m.f of the following
(a) Cu2+(aq) (0.0001M)/Cu(s); E0 = +0.34V Zn2+(aq) (0.01M)/Zn(s);
0
E = -0.76V
(b) Na+(aq)(0.001moldm-3)/Na(s); E0 = -2.71V Fe2+(aq) (0.2moldm-3)/Fe(s);
0
E = -0.44V
2+
(c) Sn (aq)(1.00M)/Sn(s); E0 = -0.14V Mn2+(aq)(0.01M)/Mn(s); E0
= -1.18V
(d) Ca2+(aq) (2.00moldm-3)/Ca(s) E0 = -2.76V Cu2+(aq)(0.02moldm-3)/Cu(s)
0
E = +0.34V
(e) Mn2+(aq)(0.030M)/Mn(s); E0 = -1.18V Cu2+(aq) (0.002M)/Cu(s) E0
= +0.34V
2. Calculate the Ecell for the reaction: 2Al(s) + 3Mn2+(aq)  2Al3+(aq) + 3Mn(s) E0cell = + 0.48V
Given that [Mn2+] = 0.50M and [Al3+] = 1.50M

3. Determine the Ecell based on these half equations

VO2+(aq) + 2H+(aq) + e-  VO2+(aq) + H2O(l) E0 = 1.00V
Zn2+(aq) + 2e-  Zn(s) E0 = -0.76V
+ +
Given that [VO2 ] = 2.0M [H ] = 0.50M [VO2+] = 0.002M [Zn2+] =
0.1M

DIFFERENCES BETWEEN PRIMARY AND SECONDARY CELL

Primary cells are those in which current is produced as a result of an irreversible
chemical change. Once they are used up, primary cells cannot be recharged. The electrolytes
and the electrodes used have to be replaced each time they wear out. Example of primary
cells are Daniel cell and Leclanche cell. They are used in lighting up torch-bulb, driving a toy
vehicle, in radios e.t.c. Other examples of primary cells are silver cells (used in electronic
watches and hearing aids), Alkaline cells, Mercury cell. e.t.c

Secondary cells are those in which current is produced by a chemical change which is
reversible. They are also known as accumulators. Secondary cells can be recharged by driving
a current through them in the opposite direction to the flow of current it normally produces.
This is usually done by passing a direct current through them. Examples of secondary cells
are lead acid accumulators or Nife batteries. They are used in car batteries, handsets, laptops
e.t.c.
PRIMARY CELL SECONDARY CELL
Cannot be recharged Can be recharged
Does not produce a steady current Produces a steady current

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The Daniel Cell
The Daniel cell is a primary cell cell which consist of copper vessel filled with a saturated
solution of copper(ii) tetraoxosulphate (vi) and a porous pot filled with a zinc
tetraoxosulpahate (vi) solution into which a zinc rod is immersed. The copper vessel acts as
the cathode, while the zinc rod acts as the anode in a Daniel cell. (Helpful Mnemonics:
DaCuZn)
The e.m.f of the Daniel cell at the initial stage is 1.1v. It is a primary cell and therefore
cannot be recharged. It has to be replaced after use.
The Daniel cell is used in digital and analogue watches, radios e.t.c

The Lechlanche Cell

The anode of a lechlanche cell is made up of a Zinc rod, while the cathode is a carbon rod.
Ammonium chloride solution acts as the electrolyte in a wet lechlanche cell while ammonium
chloride paste is the electrolyte in a dry lechlanche cell. (Helpful Mnemonics: LeCaZn)
At the anode, zinc atoms lose two electrons and becomes dissolved as zinc (ii) ions
Zn(s)  Zn2+ + 2e-
At the cathode, the ammonium ions accepts the electrons and get reduced to ammonia and
hydrogen gas.
2NH+4(aq) + 2e-  2NH3(g) + H2(g)
The hydrogen gas produced is removed constantly by manganese (iv) oxide in order to
prevent it from adhering or attaching to the cathode. The lechlanche cell is used in torches,
bicycle lamps, radio. The Lechlanche cell is a primary cell, and would also have to replaced
once it is used up.

Lead Accumulator
This is a secondary cell. They are also known as storage cell. Lead accumulators are mostly
used as car batteries and they usually charged by passing a direct current through them. In
accumulator that is fully charged, the cathode is lead(iv) oxide¸ while it anode is a
metallic lead. The electrolyte is a solution of dilute tetraoxosulphate(vi) acid,
H2SO4. The cell usually gets discharged, when the two electrodes are connected to an
external circuit, thereby producing electricity.
During the discharging process, the metallic lead atoms at the anode release two electrons
to become oxidized as lead(ii) ions.
Pb(S)  Pb2+ + 2e-
This Pb2+ then combines with tetraoxosulphate(vi) ions (SO 42-), in the electrolyte to become
deposited on the anode as insoluble lead(ii) tetraoxosulphate(vi) PbSO 4,
Pb2+(aq) + SO42-(aq)  PbSO4(s)
10 | P a g e
The electrons released at the anode are accepted at the cathode where lead (iv) oxide and
hydrogen ions gets reduced to lead(ii) ions and water.
PbO2(s) + 4H+(aq) + 2e-  Pb2+(aq) + 2H2O(l)
The lead (ii) ions then combines with the SO 42- ions in the electrolyte to become deposited as
insoluble PbSO4 at the cathode.
Pb2+(aq) + SO42-(aq)  PbSO4(s)
During the discharging process, two things happens,
(i) the density of the acid decreases to from 1.25gcm -3 to 1.15gcm-3. This is due to the
absorption of some hydrogen ions and tetraoxosulphate(vi) ions from the electrolyte
(ii) The e.m.f of the cell drops from 2.2v to 1.8v
When both electrodes are completely covered with white deposits of PbSO 4, the lead
accumulator will stop producing electric current. It must therefore be recharged before it can
start producing current again.
On recharging, electrolysis occurs and the reactions at the respective electrodes are
reversed. The electrode which is the anode in the charged cell becomes the cathode on
recharging and the cathode of the charged cell becomes the anode on recharging. During
recharging, the anode of an external electrical source are connected to the cathode of the
cell, while the cathode of an external electrical are connected to the anode of the recharging
cell. At both the anode and the cathode, the PbSO 4(s) is ionized back into Pb 2+ and SO42+. But
Pb2+ is reduced to metallic lead at the cathode of the recharging cell while the Pb 2+ of the
anode is oxidized to PbO2(s) and H+.
At the cathode: PbSO4(s)  Pb2+ + SO42-
Pb2++ 2e-  Pb(s)
At the anode: PbSO4(s)  Pb2+ + SO42-
Pb2+(s) + 2H2O(l) + 2e-  PbO2(s) + 4H+(aq)
The e.m.f of the cell then returns to the original value of 2.2V while the density returns to the
original 1.25gcm-3.

ELECTROCHEMICAL SERIES
Electrochemical series is an arrangement of chemical elements or ions in order of their
standard electrode potential starting from the most negative to the most positive determined
under specific conditions. Strongly electropositive ions (usually metals) are at the top of the
series while strongly electronegative ions (usually non-metals and oxidizing agents) are at the
bottom of the series.
The relative position of ions in the electrochemical series.

CATIONS ANIONS

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 K+ If two cations areIf two anions are OH-
Na + present in anpresent in I-
electrolyte theelectrolyte, the
Ca2+ Br-
cation below theanions that is above
Mg2+ other one in thethe other one in the Cl-
Al3+ electrochemical electrochemical
Zn2+ series will be series will be
Fe2+ preferentially preferentially NO3
Sn2+ discharged. discharged
SO42-
2+
Pb
H+
F-
2+
Cu
Hg2+
Ag+
Au3+
Pt2+

The Importance of electrochemical series

1. Predicting the preferential discharge of ions in electrolysis. Metal down the series
is preferentially discharged to the one above it and the non-metal higher in the series is
discharged in preference to the ones below it.
2. Chemical reactivity of elements: metals in the series are arranged in decreasing order
of chemical reactivity except for calcium which is less reactive than sodium but is above
sodium.
3. Natural occurrence: metals above hydrogen in the series do not occur in the free state
instead, they exist as compounds e.g. chlorides, sulphides, oxides etc.
4. Displacement and redox reactions: the series shows at a glance the order in which
element will displace another. Metals will displace metals which are below them in the
series. For redox reactions, reducing power of elements decrease down the reactivity
series while their oxidizing power increases down the series.
5. The Direction of current flow and the magnitude of the e.m.f. of cell: The metal
higher up in the series will serve as negative electrode while that lower in the series will
serve as positive electrode. A powerful cell with a big e.m.f is produced by using metallic
electrode which are widely far apart in the electrochemical series.

Limitation of Electrochemical series

The following are the limitations of electrochemical series
4. It cannot be used to predict the rate at which a reaction will occur

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5. It cannot reveal the amount of materials reacting
6. Since the E.C.S relate only to standard conditions, it values are slightly affected by
changes in concentration, temperature and pressure.

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