ELECTROCHEMISTRY

This is the aspect of Chemistry which deals with the ability of substances to allow the passage or transfer of
electricity through them.
The transfer of electricity through a substance is known as electrical conduction.
Electrical conduction is classified into two:
1. Electronic Conduction: This is the transfer of electricity in metallic element through free mobile electrons in
the lattices of metals .i.e electrons are carrier of electric current.
2. Electrolytic Conduction: This is the transfer of electricity in ionic compounds through free mobile ions. i. e
carrier of electricity are free mobile ions.
ELECTROLYSIS
Electrolysis is the decomposition of an ionic compound or polar covalent molecule by passage of direct current
through the aqueous solution or molten form of the compound [through conductors known as electrodes].
ELECTROLYTES
These are ionic compounds/polar covalent molecules which decomposed when direct current is passed into
the aqueous solution or molten form of the compound through the electrodes.
CLASSIFICATION OF THE ELECTROLYTES
Electrolytes are classified into three:
A. Strong Electrolytes: These are compounds which decomposed and ionize completely in aqueous solution
to produce free mobile ions. These substances are non-conductor when they are in solid state (since the ions
are in fixed position in their crystal lattice).
Examples are :
I. Dilute strong mineral acids E. g HCl(aq) ; HNO3(aq) ; H2SO4(aq) ; HI(aq)
II. Solutions of strong alkalis E.g KOH(aq); NaOH(aq)
III. All soluble salts E.g NaCl(aq) ; KCl(aq) ; NH4Cl(aq) ; Pb(NO3)2(aq) etc
Strong electrolytes ionize completely as follows:
KOH(aq) K+(aq) + O H - (aq)
HNO3(aq) H+(aq) + NO3 - (aq)
Pb(NO3)2(aq) Pb2+(aq) + 2NO3 - (aq)
Na2SO4(aq) 2Na+(aq) + SO42- (aq)
B. Weak Electrolytes : These are compounds that ionize only slightly in aqueous solution to produce free
mobile ions. The quantity of ions produced by weak electrolyte per molecule is relatively low compared to
that produced by strong electrolytes. Hence, weak electrolytes have lower conductivity compared with strong
electrolyte. Examples are:
I. Natural / Organic acids E.g CH3COOH; HCOOH; (COOH)2 etc.
II. Solution of Weak alkalis E.g NH4OH(aq) ; Ca(OH)2(aq) ; water
Weak Electrolytes ionize partially as illustrated below:
CH3COOH(aq) CH3COO – (aq) + H+(aq)
NH4OH(aq) NH4+ (aq) + O H - (aq)
2H2O H3O+(aq) + O H - (aq).
C. Non-Electrolyte:
1
These are pure covalent molecules which are not capable of producing free mobile ions. Examples of non-
electrolytes are: Urea; ethanol; benzene; starch; cellulose; glucose etc.
DIFFERENCES BETWEEN ELECTROLYES AND CONDUCTORS
Conductors Electrolytes
They are metallic elements / graphite They are ionic compounds
They are solid except Hg(liquid) They are in molten form or aqueous solution
They contain free mobile electrons They contain free mobile ions
Physical changes occur during the passage of Chemical changes occur during the passage of
electric current electric current
Does not undergo decomposition Undergoes decomposition
Conduct easily at lower temperature Conduct easily at higher temperature.

ELECTRODES
Electrodes are conductors (Solid poles) through which an electric current enters of leaves the electrolytes.
Electrodes are classified into two:
I. cathode and II. Anode
Anode : It is the positive electrode (in electrolytic cell) by which conventional current enters the electrolyte or
by which electrons leave the electrolyte. It is the electrode which is joined to the positive terminal of the
electric supply (battery).
Cathode: It is the negative electrode by which conventional current leaves the electrolyte or by which
electrons enter the electrolyte. It is the electrode which is joined to the negative terminal of the electric supply
(battery).
ELECTROLYTIC CELL
This is the assembly of two electrodes in an electrolyte. It enables oxidation and reduction reaction.
Oxidation occurs at the anode (positive electrode) while reduction occurs at the cathode (negative electrode).
Another name for electrolytic cell is Voltammeter
ELECTROLYTIC CONDUCTION
When an electrolyte is in solution, the ionic lattice is broken down and the ions are free to move under the
influence of the field.
Positive ions (Cations) are attracted towards the negative electrode where they accept electrons and undergo
Reduction: Mx+ + xe- M.
The cathode is reducing agent is a reducing agent (electron donor) because it donates electrons to the ions
migrates to it.
Negative ions (anions) are attracted towards the positive electrode (anode) where they give up (donate)
electrons and undergo oxidation: i.e Nx- N + xe-
The anode is an oxidizing agent (electron acceptor) because it accepts electrons from ions that migrate to it.
NOTE THAT:
I. In electrolytic cell, the anode is the positive electrode while the anode of the battery is negative.
Also, the cathode electrode is negative while the cathode of the battery is positive.

II. Electrons flow is in the opposite direction to the flow of current as indicated in an electrolytic cell below:
2
 Battery (source of current) Electron flow (e-)
e-

Direct current ( I )
I
A
Cathode
Anode + _
(R.A)
(O.A)

Electrolyte

Anion Nx- Mx+ Cation

Electrolytic cell

ELECTROLYTIC PROCESSES
Electrolytic processes involves three steps:
1. Ionization of electrolyte and water (if aqueous solution) or electrolyte alone (if in molten form)
Examples are
i. Aqueous Pb(NO3)2
Pb(NO3)2(aq) Pb2+(aq) + 2NO3-(aq)
H2 O H+(aq) + OH-(aq)
ii. Molten CaCl2
CaCl2(s) Ca2+ + 2Cl-
2. Migration of ions to the electrodes: The positively charged ions migrate to the cathode and negatively
charged ions migrate to the anode.
Examples to cathode to anode
2+ -
Pb(NO3)2 Pb (aq) 2NO 3(aq)
+
H2 O H (aq) OH-(aq)

3. Discharge of ions at the electrodes: The discharged of ions involve gain of electrons (reduction) at the
cathode and loss of electrons (oxidation) at the anode e.g.
At the cathode
Pb2+ + 2e- Pb(S) (reduction)
At the anode
2Cl- Cl2 + 2e- (oxidation)
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 For cases where two different ions having the same charge type migrate to an electrode, one of the
ions is selected for preferential discharge.
The selection of an ion for preferential discharge at an electrode is based on three factors.

FACTORS AFFECTING SELECTIVE DISCHARGE OF IONS IN ELECTROLYTIC CELL

1. Position of Ion In the Electrochemical Series: An ion lower in the electrochemical series is selected for
preferential discharge over the one above, if the solution of the electrolyte is dilute. E.g consider the
electrolysis of dilute NaCl(aq)
Electrolyte at cathode at anode
+
NaCl Na Cl-
H2 O H+ OH-
At the cathode
Hydrogen ion discharges at cathode because H+ is lower in the activity series than Na+ i.e
H+ + e - H; H+ + e- H
H + H H2(g)
OR
+
2H + 2e- H2(g)
At the anode
OH- discharges at anode because OH- is lower in the activity series than Cl-
OH-(aq) OH+ e-; OH-(aq) OH+ e-
OH +OH H2O(l) +O
O + O O2
OR
-
4OH (g) 2H2O(l))0 + O2(g) +4e-

ELECTROCHEMICAL SERIES/ ACTIVITY SERIES

Cations
4 Anions
K+
Ca2+
Na+
F-
 Al3+ SO42-
Zn2+
Fe2+ 2+ NO3-
Sn
Pb2+ Cl-
H+
Cu2+ Br-
Hg+ I-
Ag+
To Cathode OH- To Anode
Au +

For Example
Electrolysis of CuSO4(aq) using (graphite or pt) electrode
CuSO4(aq) Cu2+(aq) + SO42-(aq)
H2 O H+(aq) + OH-(aq)
At cathode Cu2+ will discharge being lower in the activity series.
At the anode OH- discharged because of its lower position in the series.
At cathode At the anode
2+ - -
Cu + 2e Cu(s) OH OH + e-; OH- OH + e-
OH+ OH H2 O + O
O+O O2(g)
Over all reaction
2Cu2+(aq) + 4e- 2Cu(s)
-
4OH (aq) 2H2O + O2(g)+4e-
Nature of the resulting solution after the process
Cu is removed at cathode
OH- is removed at anode
H+ and SO42- remain in solution and hence combine to form H 2SO4 which is acidic and the blue colour of the
solution is discharged then the solution becomes colourless.

Further examples
Electrolysis of Dilute NaOH, NaCl, CuCl2 using (c or pt) electrodes
2. Nature of Electrode:
Generally, electrode are expected to be inert (i.e. not react with ions). Certain electrodes take part in
electrolytic reaction either by reacting with the ions or the product formed.
Platinum (Pt) and graphite(c) usually behave as inert electrodes however, pt is attacked by chlorine and
graphite is attacked by oxygen.

5
Hence, Carbon electrode is not advisable to be used at anode which oxygen gas is to be produced at anode.
Electrodes which have strong affinity for certain ion may influence the selective discharge of the ion e.g. in the
electrolysis of aqueous NaCl(aq) using pt electrodes, H+ are discharge at the cathode.
If a mercury cathode (Hg) is used however, the mercury will associate with Na + to form sodium amalgam
(Na/Hg) since Hg has strong affinity for Na +. Hence the discharge of Na + requires less energy than the discharge
of H+ because of the mercury electrode used.
Na+(aq) + Hg(l) + e- Na/Hg
In some cases, electrodes which have character similar to the ion of the electrolyte also influence the
discharged of ion e.g. in the electrolysis of CuSO 4(aq), using copper electrodes, neither the So 2-4 nor OH- will
discharge instead, the copper atoms from the anode will go into the solution as Cu 2+ since Cu2+ have greater
tendency to give up (donate) electrons more readily than So 2-4 or OH-. Therefore copper anode will dissolve
and migrate to cathode to discharge and deposit on cathode.
This principle is applicable in the purification and extraction of metals.

3. Concentration of The Ions in the Electrolyte:

This is the third factor that affects the discharge of ions in the processes of electrolysis. An increase in
the concentration of the ion tends to promote its discharge from solution if others factors are constant,
and if ions are closed in the electrochemical series.
Examples
In the electrolysis of brine (conc. NaCl(aq) .the solution contains four types of ions.
Cathode anode
+
NaCl Na Cl-
H2 O H+ OH-
Consider the position of two cations (Na+ and H+) as well as the two anions (Cl- and OH-)
At cathode
Na+ is the higher in the series and further apart well from H + so; concentration has no effect on the
discharge of Na+. Hence H+ is discharged since it is lower in the activity series.
At the anode
Cl- and OH- migrate to the anode since OH- suppose to discharged because of its position in the activity
series but both ions are closed in the electrochemical series and Cl - is of higher concentration, Cl- is then
-
discharged in preferential to OH .

EXERCISE:
State the products at each electrodes and nature of the electrolyte after the electrolysis of the following
compounds.
(a) Dilute NaOH using platinum electrodes (pt)
(b) Dilute NaOH using mercury electrodes
(c) Dilute CuSO4 using carbon electrodes
(d) Dilute CuSO4 using copper electrodes
(e) Conc. CaCl2 using pt electrodes & carbon electrode

6
(f) NaCl using platinum electrodes & carbon electrode
(g) Conc. NaCl using carbon electrodes.
EXAMPLES OF ELECTROLYSIS
1. Electrolysis of acidified water i.e. little quantity of H 2SO4 is added to water.
Pt/c pt
Compounds at cathode at anode
+
Dil. H2SO4 2H
SO42-(aq)
Water H2O H+(aq) OH-(aq)
At Cathode
H+ migrate to the cathode where they acquire an electron each to form neutral hydrogen atoms.
These atoms combine in pairs to produce the diatomic molecules of gaseous hydrogen.
H+(aq) + e- H H+(aq) + e- H
H + H H2(g)
+ -
4H (aq) + 4e 2H2(g)
At anode
Both SO42- and OH- migrate to the anode where OH- are preferentially discharged, each OH - loses
an electron to the anode to become a neutral, OH group.
Two OH groups react to form one molecule of water and one atom of oxygen .Two oxygen atoms
combines to give diatomic molecules of oxygen gas.
OH-(g) OH+ e- ; OH-(g) OH+ e-
OH + OH H2O(l) + O
O + O O2
Summary
4OH-(g) 2H2O(l) +O2(g) +4e-
The electrolysis of acidified water yield 2 volumes of hydrogen at the cathode and 1 volume of oxygen
at the anode. i.e oxygen : hydrogen 1:2
The nature of the electrolyte at the end of the process is that, the solution became concentrated
because the process is amount to removal of water.

2a. Electrolysis of copper (II) Tetraoxosulphate (VI) solution (using different anodes).
The electrolytic cell used is designed to collect solid copper deposits at the cathode and a gas at the
anode.
(with pt or c electrodes)
At cathode at anode
2+
CuSo4 Cu (g) SO42-
H2 O H+(aq) OH-(aq)
At cathode.
Cu2+ discharged preferentially (position on the electrochemical series)
Cu2+ +2e- Cu(s);

7
 2Cu2+ + 4e- 2Cu(s)
At anode using(c or pt)
OH- is preferentially discharged (position in electrochemical series)
OH-(g) OH + e- ; OH-(g) OH + e-
OH +OH H2O(l) + O
O+O O2
-
4OH (g) 2H2O(l) + O2(g) + 4e-
Overall
2Cu + 4OH-(aq)
2+
2Cu(s)+ O2(g) + 2H2O(l)
Products:
At cathode :brown copper
At anode: oxygen gas.
Nature of the resulting solution
As the process continue, the solution become acidic with Tetraoxosulphate VI acid increase in concentration
due to the H+ and SO4 2- which remain in the solution there will be gradual fading away of the blue colour of
Cu2+(aq) until the solution become colourless.
2b. Electrolysis of CuSO4 with the copper electrodes, when copper is placed at anode and the electrolyte is
CuSO4 , there are three possibility SO42- may discharge, OH- may discharge, metallic atoms on the anode
surface may dissolve in the solution as ions leaving their electrons behind. Cu (s)----- Cu2+(aq)+2e-
The conversion of copper atoms to ions is favoured as it requires the least energy, so no ions are
discharged at anode, but for each atom of copper deposited at the cathode one atom of copper is dissolved
from the anode to form Cu2+. Hence there is no change in colour of the electrolyte since Cu 2+ is merely
transferred from anode to cathode during the electrolysis.
Anode: Cu (s) Cu (aq) 2+ + 2e-
Cathode: Cu (aq) 2+ + 2e- Cu(s)
Anode Electrolyte Cathode
- 2+ -
Cu(s) - 2e Cu (aq) +2e Cu(s)
3. Electrolysis of dil. sodium chloride solution with carbon or graphite electrodes.
Cathode Anode
+
NaCl Na (s) Cl -(g)
H2 O H+(aq) OH-(aq)
At cathode
H+ being lower in the electrochemical series is discharge in preference to Na +
H+ + e - H; H+ + e - H
H+H H2(g)
OR
- -
4H + 4e 2H2(g)
At Anode using Pt
Both Cl- and OH- moved to the anode but OH- discharge based on the position on (ecs)
OH- OH + e- ; OH- OH + e-
8
 OH + OH H2O + O
O+O O2(g)
-
4 OH 2H2O(l) + O2(g) + 4e-
Summary
Nature of the resulting solution
The resulting solution produced concentrated NaCl as H + and OH- ions of water are discharged from
solution.

LAWS OF ELECTROLYSIS
Faraday’s first Law of Electrolysis
It state that the mass (m) of an element discharge during an electrolysis is directly proportional to
the quantity of electricity (Q) passing through it.

i.e. m Q
But Q = it

m it
m = Eit where
m = mass (g)
q = quantity of electricity (unit- c coulomb)
I = current (amperes)
T = time (seconds)
The law can also be stated as the mass of an element discharged during electrolysis is directly
proportional to
- The magnitude of the current and
- The time of flow of the current
m = Mass
E = Electrochemical equivalent of the substance
Graphically it can be shown as follow:

m(g) m(g)

Time (sec) current (A)

NOTE THAT:
I. 1 Faraday of electricity (1 F) = 1 mole of e- = 96500 coulombs (96500C)
II. Mass of 1 mole of an atom is the atomic mass of the element.
9
Examples
1. How many coulombs of electricity are passed through a solution in which 6.5 amperes to run for 1.0
hour? (JAMB 1986)
Solution
Q = It, time = 1x60 x 60 = 3600 sec
Q = 6.5 x 3600 = 23400 coulombs
2. Copper II tetraoxosulphate VI solution is electrolyzed using platinum electrodes. A current of 0.193A
was passed for 2 hours. How many grams of copper are deposited? (cu = 63.5, f = 96500 c) [JAMB
1995]
Solution
I = 0.193A
t = 2x 60 x 60 = 7200 sec
Q = it = 0.193 x 7200 = 1389.6C
But
Cu +2e
2+ -
Cu
2F 63.5g or Cu
i.c 2x96500C = 63.5g
1389.6C = 63.5 x 1389.6
2x 96500
= 0.46g or Cu was deposited

3. [WEAC 2006] a solution of CuSO4 was electrolyzed between pure copper electrodes and the following
results were obtained.
Mass of copper anode before experiment = 7.20g
Mass of copper anode after experiment = 4.00g
Mass of copper cathode before experiment = 5.75g
From the information provided:
(1) Calculate the mass of the cathode, after the experiment
(2) If the electrolysis was carried out for 1hr 20minutes with a 2 ampere determines the value of
Faraday’s
Solution
I. Mass of the copper that dissolve form the anode = (7. 20 – 4.00)g = 3.20g
Mass of the copper cathode after experiment = (5.75 + 3.2) g = 8.95g
II. t = (60 x 60 x 1)+(20 x60) = 4800 sec
I = 2.0 A
Q= It = 2x 4800 =9600 C
1F = 96500 C
96500 = 1F

 9600C = = 0.1F
4. [NECO 2008]

10
 5.6dm3 of oxygen gas was evolved at the anode during the electrolysis of dilute copper (II)
Tetraoxosulphate (VI) using platinum electrode. What mass of copper is deposited at the cathode during
the process?
(Cu=64, MGV at S.T.P=22.4dm3, IF=96500c)
Solution
1st determine the quantity of electricity that flows.
At anode:
4 OH- 2H2O + O2 + 4e-
From this equation 4 moles of electrons produce 1 mole of oxygen i.e 4F.
4F = 22.4dm3 of oxygen
22.4dm3 = 4 x 96500C
5.6 dm3 = 4 x 96500 x 5.6 = 96500C
22.4
Q that was used = 96500C
Cu2+ + 2e- CU (s)
2F = 64g
2 x 96500C = 64g
 96500C = 64 x 96500
2 x 96500
= 32.0g
CLASS WORK
1. 0.222g of a divalent metal is deposited when a current of 0.45 ampere is passed through a solution of its
salt for 25 minutes using appropriate electrodes. Calculate the relative atomic mass of the metal (1F =
96500C)
2. 0.1 Faraday of electricity deposited 2.95g of nickel during electrolysis of aqueous solution. Calculate the
number of moles of nickel that will be deposited by 0.4F (Ni =58.7)
3. Calculate the volume of oxygen evolved at 285K and 0.91x105 NM-2 when a current of 2.5A is passed
through an acidified water for 1.5minutes {MV =22.4dm3mol-1 s.p =1.01x105 NM-2 ; 1F=96500C}
4. A non-metal of relative atomic mass of 16 is deposited by electrolysis. If 0.34g of the non-metal is
deposited on the anode when 0.45ampere flows for 2.5 hours. What is the magnitude of the charge on
the anion of the non-metal?
5. In the electrolysis of aqueous aluminium III chloride, a current of 3.5 amperes was passed for a period of
3 hours.
(i) What volume of chlorine gas measured at s.t.p is produced?
(ii)What mass of the metal is deposited at the cathode? {Molar volume of any gas at s.t.p is 22.4dm 3mol-
1
]
6. List the factors which affect the discharge of ions during electrolysis
b. The following data were collected in an experiment on electrolysis
Current I (A) Time (sec) Q (Coulombs) Mass deposited
0.20 900 0.06
0.20 1800 0.12
0.20 2,700 0.18
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 0.20 3,600 0.24
1. Copy and complete the table by calculating the quantity of electricity passed in each case.
2. Plot the graph of the mass M deposited against the quantity of electricity Q, passed.
3. From the graph determine the mass of M that was deposited by the same current passing for 20
minutes.
4. From the shape of the graph, which of the laws of electrolysis does the experiment identify?

FARADAY SECOND LAW OF ELECTROLYSIS

It state that, when the same quantity of electricity is passed through different electrolytes, the relative
number of moles of the elements discharged are inversely proportional to the charges on the ions of
the elements
Assignment:
Describe an experiment to verify the Faraday 2nd law of electrolysis

Example [JAMB 1981]

The same current is passed for the same time through solutions of AgNO 3 and CuSO4 connected in series.
How much silver will be deposited if 1.0g of copper is produced (Cu=63.5, S=32.0, O=16, Ag=108,
N=14)
Solution
CuSO4 AgNO3
2+ -
Cu + 2e Cu(s) Ag + + e- Ag(s)
2F = 63.5g 1F = 108g
63.5g of Cu = 2 x 96500 i.e 96500 = 108
1.0g of Cu = 2 x96500 x 1.0 C  3039.37C = 108 x 3039.37
63.5 96500
= 3039.37C. = 3 .40g of Ag
CLASS WORK
A current of 20 amperes flows for 5 hours through three cells in series. They contain solutions of
sodiumtrioxonitrate V, mercury II tetraoxosulphate VI and aluminium tetraoxosulphate VI. Calculate the mass
of the metal deposited in each cell {Na=23.0; Al=27.0, Hg=200.6}

USES/ APPLICATIONS OF ELECTROLYSIS

It is used in extraction of metals and production of some non-metals e.g. H 2(g), F2(g), Cl2(g), O2(g) i.e. from
electrolysis of their ores, fused compounds or aqueous solution.
1. It is used for purification of metals e.g. (Cu, Hg, Ag & Au).
2. It is used for protecting some metals from corrosion by electroplating another metals on them.
3. It is used for preparation of some important compounds e.g. NaOH,

12
 PURIFICATION OF METAL
The metal to be purified is made the anode and the pure form of the same metal is made the cathode.
The electrolyte is made up of aqueous solution of the salt of the same metal e.g
Extraction of copper metal produces impure copper. The impure copper can be purified by electrolysis
The impure copper is made the anode while the pure copper is made the cathode while the electrolyte
is copper II tetraoxosulphate VI solution 0r any soluble salt of copper.
During the electrolysis impure copper dissolves at anode, the copper ions migrate to Cathode and get
reduce at Cathode and deposited at the Cathode as pure Copper. The impurity settled down at the
bottom of the anode in the container.
At Anode At Cathode
- 2+ -
Cu(s) -2e Cu + 2e Cu(s)
Or
Anode Electrolyte Cathode

A
Cathode
+ _ (Pure copper)
Anode
impure ore of Cu Deposit of pure copper

Impurity
CuSO4(aq)

Purification of copper

ELECTROPLATING
The process involves coating one metal with another metal that has good appearance or does not
corrode easily e.g electroplating of spoon.
At cathode – metallic object to be coated (spoon)
At anode – strip of the plating metals (silver)
Electrolyte – salt of the plating metal (soluble salt)
At anode at cathode
- + -
Ag(s) - e Ag + e Ag(s)

A
13
+ _
Anode (Silver) Cathode
Silver electroplated spoon
 AgNO3(aq)

Silver Electroplating of Spoon

ELECTROCHEMICAL CELL
This is a device that converts the chemical energy to electrical energy. The flow of electrons can be
set up between two electrodes which have different electrode potential.
The magnitude of the current produced is determined by the difference between the two
electrodes potential. This is as a result of speed and the readiness of election flow.
Note: That current flow in the opposite direction to the flow of electrons examples of
electrochemical cell are voltaic cell or galvanic cell. The emf of a cell is related to Gibb’s free energy
change by the equation ΔGθ = - nFEθ
Where ΔGθ = standard fee energy change
n = number of moles of electrons
F = Faraday’s constant
Eθ = Standard electrode potential

DIFFERENCES BETWEEN ELECTROLYIC CELL AND ELECTROCHEMICAL CELL

14
 ELECTROLYIC CELL ELECTROCHEMICAL CELL
Salt bridge is not needed Salt bridge is required
Cathode is –ve while anode is +ve electrode Cathode is +ve while anode is -ve electrode
Only one electrolyte is required Two electrolytes are used
Electrodes are in the same compartment Electrodes are in separate compartment
Electrons are forced by external source e.g battery Electrons are produced as a result of oxidation at an
electrode (anode)
It converts electrical energy into chemical energy i.e It converts chemical energy to electrical energy i.e
electric current is needed for reaction to occur chemical reactions generate electricity.

ELECTRODE POTENTIAL
Electrode potential of metal ion / metal system is the potential difference set up between the metallic
electrode and electrolyte solution.
It is not possible to measure the absolute value of an electrode potential directly,
Instead, it must be measured against some reference standard.
Hydrogen has been chosen internationally as an arbitral standard, with an electrode potential of Zero
at all temperatures. The electrode potential of a given metal ions/ metal system is then expressed in terms of
the potential difference ( in volts) which exist in between the metallic electrodes and the standard
hydrogen electrode. This is known as the standard electrode potential of the metal ions/ metal system on
hydrogen scale.
Standard Hydrogen Electrode Potential SHE

The standard hydrogen electrode consist of hydrogen gas 25 or 298k and one atmospheric
pressure, bubbling around an inert platinum electrode in contact with a one – molar solution of hydrogen
ions i.e 2H+ (aq) / H2(g) system.

H+(aq) / H2(g)

H2(g) at 250 C and 1atm

Platinum electrode

1.0 M/ 1.0 moldm-3 H+

Standard Hydrogen Electrode

The electrode potential value is
- Positive if electrons flow from the hydrogen electrode to the metal electrode
- Negative if electrons flow from the metal electrode to the hydrogen electrode

15
 Standard Electrode Potential Eθ
The standard electrode potential Eθ is a measure of 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 ( 298K and 1atm
pressure and 1.0 molar concentration). OR
The standard electrode potential of a metal ion /metal system is the p.d set up between the metal and
a one-molar solution of its ions at 25 0C arbitrarily taking the standard electrode potential of Hydrogen
ions/Hydrogen gas system as zero [0] volt .
The electrode potential of a given system depends on:
- Overall energy change
- The concentration of ions in the electrolyte solution
- The temperature.
- The pressure

MEASUREMENT OF STANDARD ELECTRODE POTENTIAL

To measure the standard electrode potential of metal ion/metal system, the half cell of the system i.e. metal
rod is dipped in metal solution and then connected to the system called standard hydrogen electrode by a salt
bridge.
The potential difference between the two half-cells is known as the electromotive force (e.m.f) of the cell. The
e.m.f. is a measure of the tendency for electrons to flow from one cell to another.

At anode Zn → Zn2+ + 2e- oxidation

+ -
At cathode 2H + 2e → H2 Reduction
Since Zn is above H, Zn atom can easily be oxidized than Hydrogen.
Overall reaction is
s Zn(s) + 2H+→ Zn2+(aq) + H2(g)
The cell notation is Zn(s)/Zn2+(aq) //2H+(aq)/H2(g)
N.B.
A single / indicates the interface between solid electrode and solution.
A double // indicates the salt bridge.
Example 2

16
At anode H2→ 2H+ + 2e- oxidation
2+ -
At cathode Cu + 2e → CuReduction
Since H is above Cu, H can easily be oxidized than Cu
Overall reactions is H2 + Cu2+→ 2H+ + Cu
The cell notation is H2(g) / 2H+(aq) // Cu2+(aq) / Cu

**N.B. When the electrode potential of a metal ion/metal is negative relative to hydrogen ion/hydrogen
system, it implies that electrons flow through the external current from the metal e.g. Zinc to the hydrogen
electrode. Hence, it is easier for hydrogen ion to be reduced than the metallic ion.
i.e 2H+(aq) + 2e- H2(g)
2+ -
Zn Zn + 2e
Also, when the electrode potential of a metal ion / metal system is positive relative to hydrogen ion /
hydrogen system, it implies that electrons flow through the external circuit from hydrogen to the metal
electrode. Hence, it is easier for metal ions to be reduced than the hydrogen ion
Cu2+ 2e- Cu
H2 2H + 2e-
+

Producing An electric current

A flow of electrons (i.e. an electric current) can be set up between 2 electrodes which have different electrode
potentials.

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As indicated above, metallic Zinc is in contact with Zinc ions, and metallic copper with copper (II) ions. An
electric current flows through the wire which connects the two metals or electrodes outside the solution.
 Oxidation half-cell reaction occurs at the electrode in one cell (Zinc) and
 Reduction half-cell reaction occurs at the electrode in the other half cell (Copper).
The overall redox reaction results in a flow of electrons i.e. an electric current.
The atoms of the Zinc electrode undergo oxidation and lose two electrons each to form Zinc ions which go into
the solution. The Zinc electrode becomes negatively charged and functions as the negative electrode or anode.
The excess electrons on the Zinc electrode are made to flow along the wire to the electron-deficient copper
electrode where they are taken up by the copper (ii) ions. The copper II ions become reduced by gaining 2
electrons each to form metallic copper, which is deposited on the copper electrode. The copper electrode thus
becomes positively charged and functions as the positive electrode or cathode.
NOTE: The flow of electrons from the Zinc to the copper electrode is equivalent to the flow of conventional
current in the opposite direction.
At the Zinc electrode (anode)
Zn → Zn2+ + 2e- oxidation
The anode slowly becomes depleted as the metallic zinc is converted to Zinc ions.
At the copper electrode (cathode)
Cu2+ + 2e- → Cu(s) reduction
The cathode gradually increases in size due to the deposition of metallic copper.
N.B: The net process in the cell, obtained by the algebraic addition of the two half-cell reactions, can be
represented by the following ionic equation.
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) ( Overall reaction)
The cell notation is
Zn(s) /Zn2+(aq) //Cu2+(aq) /Cu(s)

Calculation of E.m.f of the cell.

E.m.f of the cell =
Eθcell = Eθreduction - Eθoxidation OR
Eθcell = Eθcathode - Eθanode OR
Eθcell = EθRight - EθLeft

Examples
Given that:
Pb2+(aq) + 2e- Pb(s) ; Eθ = - 0.13v
Cu2+(aq) +2e- Cu(s) ; Eθ = + 0.34v
i. Write the overall cell reaction
ii. Write the cell notation
iii. Determine the e.m.f. of the cell
N.B.
The most electropositive element undergoes oxidation

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Solution
(i) Pb(s) + Cu2+(aq) Pb2+(aq) + Cu(s)
(ii) Pb(s)/Pb2+(aq) //Cu2+(aq) / Cu(s)
(iii) E.m.f. of the cell : Eθcell = Eθreduction - Eθoxidation
Ecell = [0.34 – (–0.13) ]v
= 0.34 + 0.13 = 0.47v
Some standard electrode potential values
+
K (aq) + e- K(s) E = - 2.92v
+
Na (aq) + e- Na(s) E = - 2.71v
2+
Mg (aq) + 2e- Mg(s) E = - 2.37v
2+
Zn (aq) + 2e- Zn(s) E = - 0.76v
2+
Fe (aq) + 2e- Fe(s) E = - 0.44v
2+
Sn (aq) + 2e- Sn(s) E = - 0.14v
2+
Pb (aq) + 2e- Pb(s) E = - 0.13v
2+
Cu (aq) + 2e- Cu(s) E = + 0.34v
+
Ag (aq) + e- Ag(s) E = + 0.80v
+
2H (aq) + 2e- H2(s) E = 0v

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