UNIT 2:

ELECTROCHEMISTRY
At the end of the unit, the students should be able to:

1. explain the concept of electrochemistry;

2. differentiate the types of electrochemical cells;
3. calculate the electromotive force or voltage output of some redox reaction;
4. explain Nerst equation;
5. discuss the significance of electrode potential such as:
5.1 amount of electrical energy,
5.2 free-energy change, and
5.3 equilibrium constant;
6. predict electrode products of a given electrolysis process;
7. give some applications of electrolysis;
8. explain Faraday’s Law of electrolysis; and
9. solve problems on Faraday’s Law as applied to electroplating.

29
 A car needs a battery to run, radio needs electricity from power plant or
batteries to operate and a less expensive jewelry had to be plated with gold or
silver to look lustrous and beautiful. All these are applications of electrochemistry,
a branch of chemistry that relates electricity and chemical reactions.
In this unit, the study of theoretical aspects and other applications of
electrochemical reactions will be discussed.

2.1 Electrochemical Reactions

There are two types of electrochemical reactions:
1. Those which produce electricity from chemical reactions. The process
takes place in a voltaic cell wherein the positive electrode is the
cathode and the negative electrode is the anode.
2. Those which use electricity to cause the reactions to occur. The
process takes place in an electrolytic cell wherein the positive
electrode is the anode and the negative electrode is the cathode.

Whether the cell is voltaic or electrolytic, oxidation always occurs at the

anode, while the reduction always occur at the cathode.
Oxidation-Reduction (REDOX) reactions occur simultaneously. Oxidation
involves the loss of electrons which results in an increase in the oxidation number
of the atom or ion. Reduction involves the gain of electrons which results in the
decrease in the oxidation number of the atom or ion. The substance that is oxidized
is called the reducing agent, while the substance that is reduced is the oxidizing
agent.

Examples of electrochemical reaction:

When Zn is added to a CuSO4 solution, Cu+2 ions are converted to Cu

atoms. Zn atoms enter the solution as Zn+2 ions.
0 +2 +6 -2 +2 +6 -2 0
Zn(s) + CuSO4 (aq) → ZnSO4(aq) + Cu(s)

Since the oxidation number of Zn increases from 0 to +2, Zn is oxidized; Zn

lost 2 electrons. On the other hand, the oxidation number of Cu decreases from
+2 to 0, Cu is reduced; Cu gained 2 electrons. The oxidation number of S does
not change, it is neither oxidized nor reduced.
Zn is oxidized, therefore, it is the reducing agent while Cu is reduced, and
therefore, CuSO4 is the oxidizing agent.

30
2.2 Voltaic Cells
Voltaic cell is named after Alessandro Volta who experimented on the
conversion of chemical energy to electrical energy. In spontaneous oxidation-
reduction (redox) reactions, electrons are transferred and energy is released. This
energy can do work if the electrons flow through an external device. Such setup is
called a voltaic cell. There are many examples of voltaic cell, and one of these is
the Daniel cell, illustrated below:

Figure 2.1: Daniel Cell

In the Daniel Cell:

1. The oxidation occurs at the anode.
2. The reduction occurs at the cathode.
3. The half-cell reactions are:
Negative electrode (anode): Zn(s) → Zn+2(aq) + 2e-
Positive electrode (cathode): Cu+2(aq) + 2e- → Cu(s)
4. The electrons lost by Zn move through the external circuit (Cu wire) as an
electric current to the cathode where they are gained by the Cu +2 ions.
5. When an electron flows from the anode to the cathode, the charges in each
beaker would not be balanced and the flow of electrons would stop.
Therefore, salt bridge, a U-shaped tube that contains a salt solution, is used
to keep the charges balanced. The salt bridge provides for the diffusion of
ions, the positive ions towards the CuSO4 and the negative ions towards
the ZnSO4.

31
 6. The over-all reaction is as follows:
Zn(s) → Zn+2(aq) + 2e-
Cu+2(aq) + 2e- → Cu(s)
Over-all reaction: Zn(s) + Cu+2(aq) → Zn+2(aq) + Cu(s)

The electrical current flows from the negative electrode (anode) to the
positive electrode (cathode) because there is a difference in the electrical potential
between the two electrodes. The difference in electrical potential is called an
electromotive force, emf (cell potential or cell voltage), which is measured by a
voltmeter.

2.3 Electrode Potential

The voltage or electromotive force (emf) of a cell, which is measured in
volts, is the sum of two half-cell potentials using the standard cell potential values
(E0). The standard cell potential of the cell at conditions: (1) when all of the ion
concentrations are 1 M, (2) temperature is 250C, and (3) pressure is one
atmosphere for gases. The E0 values were established by comparing the potential
of the cell with a reference cell. The hydrogen electrode whose potential is zero is
used as the reference cell. The Standard Reduction Potentials Table is presented
in Table 2.1.

Most Standard Electrode Potential tables give only one value. For example,
the given value for the forward reaction below which is reduction as obtained from
the Table 2.1:
Zn+2(aq) + 2e- → Zn E0 = -0.76
If the electrode reaction is oxidation, the reverse reaction is used and the
sign of the value is changed.
Zn(s) → Zn+2(aq) + 2e- E0 = + 0.76

The standard potential values are intensive properties, hence are not
affected by the change of stoichiometric coefficients during balancing.
For example: Suppose the reaction is multiplied by 2, it becomes:
2 Zn(s) → 2 Zn+2(aq) + 4e- E0 = + 0.76
The E0 values are useful for evaluating redox reactions. Substances with
high positive reduction potential are strong oxidizing agents (greater tendency to
be reduced) and substances with high positive oxidation potential or low reduction
potentials are strong reducing agents (greater tendency to be oxidized). As can be
seen in the table, the substances are arranged from least active metal to most
active metal. Therefore, less active metal has greater tendency to be reduced, and
more active metal has greater tendency to be oxidized.

32
Table 2.1. Standard Reduction Potentials in Aqueous Solution (1M) at 250C
E0
Half Cell Equation
Volts
F2(g) + 2e- → 2 F- (aq) +2.87
H2O2 (aq) + 2H+ (aq) + 2e- → 2 H2O +1.77
PbO2(s) + 4H (aq) + SO4 (aq) + 2e → PbSO4(s) + 2H2O +1.70
+ -2 -

MnO4-(aq) +8H+(aq) + 5e- → Mn+2(aq) + 4H2O +1.51

Stronger Weaker
oxidizing Au (aq) + 3e → Au(s)
3+ - +1.50 reducing
agent Cl2(g) +2e →2Cl (aq)
- - +1.33 agent
MnO2 (aq) +4H (aq) + 2e → Mn (aq) + 2H2O
+ - +2 +1.23
O2(g) + 4H (aq) + 4e →2 H2O
+ - +1.23
Br2(g) +2e →2Br (aq)
- - +1.07
NO3 (aq) + 4H (aq)+ 3e →NO(g) + 2H2O
- + - +0.96
Ag (aq) + e → Ag(s)
1+ - +0.80
Fe (aq) + e → Fe (aq)
3+ - 2+
+0.77
O2(g) + 2H (aq) + 2e → H2O2(aq)
+ -
+0.68
MnO4 (aq) +2H2O + 3e → MnO2(s) + 4OH (aq)
- - -
+0.59
I2(g) +2e →2I (aq)
- - +0.53
O2(g) + 2H2O + 4e →4OH (aq) - - +0.40
Cu (aq) + 2e → Cu(s)
2+ - +0.34
SO4 (aq) +4H (aq) +2e →SO2(g) +2H2O
2- + - +0.20
2H (aq) + 2e → H2(g)
+ - 0.00
Pb (aq) + 2e → Pb(s)
2+ - -0.13
Sn (aq) + 2e → Sn(s)
2+ - -0.14
Ni (aq) + 2e → Ni(s)
2+ - -0.25
Co (aq) + 2e → Co(s)
2+ - -0.28
PbSO4(s) +2e →Pb(s) +SO4 (aq)
- 2-
-0.31
Cd (aq) + 2e → Cd(s)
2+ - -0.40
Weaker Fe (aq) + 2e → Fe(s)
2+ - -0.44 Stronger
oxidizing Cr (aq) + 3e → Cr(s)
3+ - -0.74 reducing
agent Zn (aq) + 2e → Zn(s)
2+ - -0.76 agent
2H2O + 2e → H2(g) +2OH (aq)
- - -0.83
Mn2+ (aq) + 2e- → Mn(s) -1.18
Al (aq) + 3e → Al(s)
3+ - -1.66
Mg (aq) + 2e →Mg(s)
2+ - -2.37
Na (aq) + e → Na(s)
+ - -2.71
Ca (aq) + 2e → Ca(s)
2+ - -2.87
Ba (aq) + 2e → Ba(s)
2+ - -2.90
K (aq) + e → K(s)
+ -
-2.93
Li (aq) + e → Li(s)
+ - -3.05

33
 The cell potential values (Ecell) determines whether the proposed half-cell
reactions will occur or not. If the value is positive, the reaction is spontaneous and
will occur as it is written. If the value is negative, the reaction is non-spontaneous
and it will not occur as it is written, however, if the half-cell reactions are reversed,
i.e. the oxidation becomes, the reduction, the reaction will occur (if the E 0cell of the
non-spontaneous reaction is measured with a voltmeter, the reading is negative,
hence the electrode should be reversed).
The reaction is spontaneous when more reactive metal is placed in the
anode and less reactive metal is placed in the cathode. In galvanic cell, electron
will always flow from more to less reactive metal.

 Cell Representations
An electrochemical cell can be represented by
1. Using overall cell reaction:
Zn(s) + Cu+2(aq) → Zn+2(aq) + Cu(s)
2. Using the electrode reactions:
Zn(s) /Zn+2 // Cu+2 / Cu(s)
The “/” represents phase boundary and “//” represents a salt bridge.

EXAMPLES
For each of the following:
a. Write the overall cell reaction/ cell representation
b. Calculate the standard cell potential (E0)
c. Determine whether the reaction is spontaneous or non-spontaneous.
(1) Zn(s) + Cu+2(aq) → Zn+2(aq) + Cu(s)
(2) Al(s) + Mg+2(aq) → Al+3(aq) + Mg(s)

Solution:
(1) Zn(s) + Cu+2(aq) → Zn+2(aq) + Cu(s)
anode (oxidation): Zn(s) → Zn+2(aq) + 2e- E0 = + 0.76 V
cathode (reduction): Cu+2(aq) + 2e- → Cu(s) E0 = +0.34 V
Over-all cell reaction: Zn(s) + Cu+2(aq) → Zn+2(aq) + Cu(s) E0 = +1.10 V

Since Zn which is more active than Cu is placed in the anode and E0

is positive, the reaction is spontaneous.

34
(2) Al(s) + Mg+2(aq) → Al+3(aq) + Mg(s)
anode (oxidation): (Al(s) → Al+3(aq) + 3e-) x 2 E0 = + 1.66 V
cathode (reduction): (Mg+2(aq) + 2e- → Mg) x 3 E0 = -2.36 V
Thus,
anode (oxidation): 2Al(s) → 2Al+3(aq) + 6e- E0 = + 1.66 V
cathode (reduction): 3Mg+2(aq) + 6e- → 3Mg(s) E0 = -2.36 V
Over-all cell reaction: 2Al(s) + 3Mg+2(aq) → 2Al+3(aq) + 3Mg(s) E0 = -0.70 V

Since Mg is more active than Al and is placed in the cathode, thereby E0 is

negative, the reaction is non-spontaneous.
To make the reaction spontaneous, Mg must be in the anode (must undergo
oxidation) and Al must be in the cathode (must undergo reduction).

PRACTICE EXERCISE 2.1

I. For each of the following;
a. Write the overall cell reaction/ cell representation
b. Calculate the standard cell potential (Eo)
c. Determine whether the reaction is spontaneous or non-spontaneous.
1. Zn(s) + Ni+2(aq) → Zn+2(aq) + Ni(s)
2. Pb(s) + Sn+2(aq) → Pb+2(aq) + Sn(s)
3. Al / Al+3 // Mg+2 / Mg
4. Ca / Ca+2 // Cr+3 / Cr
5. Mg / Mg+2 // Fe+2 / Fe
II. In the table of standard reduction potentials, locate the half-reactions for the
reductions of the following metal ions to the metal: Sn+2(aq), Au+(aq), Zn2+(aq),
Co2+(aq), Ag+(aq), and Cu2+(aq). Among the metal ions and metals that make up
these half-reactions:
a) Which metal ion is the weakest oxidizing agent?
b) Which metal ion is the strongest oxidizing agent?
c) Which metal is the strongest reducing agent?
d) Which metal is the weakest reducing agent?
e) Will Sn(s) reduce Cu2+(aq) to Cu(s)?
f) Will Ag(s) reduce Co2+(aq) to Co(s)?
g) Which metal ions on the list can be reduced by Sn(s)?
h) What metals can be oxidized by Ag+(aq)?

35
Nonstandard Conditions
In real world applications, corrosion, a very common example of redox-
reactions occurs in nature at non-standard conditions. You may have asked “What
must we do to account for the differences that arise when standard conditions are
not present?” This situation has a clear relationship with thermodynamics. The
equation that describes cell potentials in nonstandard conditions is called the Nerst
equation:
𝑅𝑇
E = 𝐸0 − ln 𝑄
𝑛𝐹

where:
Q (in Chemical Equilibrium) – the product of the concentrations of the
products divided by the product of the concentrations of the reactants, each
concentration raised to the power of its stoichiometric coefficients.

In the equation: aA + bB ⇌ cC + dD, Q is written as:

[C]c [D]d
Q=
[A]a [B]b

96500 J
F – faraday constant , 1 F = V ∙ mol e−
n – the number of electrons transferred in the redox reaction
R = 8.313 J/(mol • K)

Using base – 10 logarithms,

2.303 𝑅𝑇
E = 𝐸0 − log 𝑄
𝑛𝐹

since Q = Keq
2.303 𝑅𝑇
E = 𝐸0 − log 𝐾𝑒𝑞
𝑛𝐹

At room temperature (T = 298K):

2.303 𝑅𝑇
= 0.0591 V
𝑛𝐹

Thus the equation becomes

0.0591 𝑉
E = 𝐸0 − log 𝑄
𝑛

or
0.0591 𝑉
E = 𝐸0 − log 𝐾𝑒𝑞
𝑛

36
EXAMPLES
1. One half – cell in a voltaic cell is constructed from a copper wire dipped into
a 4.8 x 10-3 M solution of Cu(NO3)2. The other half – cell consists of a zinc
electrode in a 0.40 M solution of Zn(NO3)2. Calculate the cell potential.
Solution:
i. Assume that the condition is at room temperature, 298K:
0.0591 𝑉
E = 𝐸0 − log 𝐾𝑒𝑞
𝑛
ii.

0.40 M Zn(NO3)2 4.8x10-3 M Cu(NO3)2

anode (oxidation): Zn(s) → Zn+2(aq) + 2e- E0 = + 0.76 V

cathode (reduction): Cu+2(aq) + 2e- → Cu(s) E0 = +0.34 V
Over-all cell reaction: Zn(s) + Cu+2(aq) → Zn+2(aq) + Cu(s) E0 = +1.10 V
iii.n = 2e-
[Zn+2
(aq) ] [0.40]
iv. Keq = [Cu+2 ] = [4.8𝑥10−3 ] = 83.33
(aq)

v. Substitute values to the working equation:

0.0591 V
E = +1.10 V − log(83.33)
2
E = + 1.04 V

2. Use the Nernst equation to calculate the cell potentials of the following cell
at 298 K:
2 Ag+(aq) (0.50 M) + Ni(s) → 2 Ag(s) + Ni2+(aq) (0.20 M)
Solution:
i. anode (oxidation): Ni(s) → Ni+2(aq) + 2e- E0 = + 0.25 V
cathode (redct’n): 2Ag+1(aq) + 2e- → 2Ag(s) E0 = + 0.80 V
Over-all cell Rxn: Ni(s) + 2Ag (aq) → Ni (aq) + 2Ag(s) E0 = + 1.05 V
+1 +2

ii. n = 2e-
[Ni+2
(aq) ] [0.20]
iii.Keq = [Ag+1 2 = [0.5]2 = 0.8
(aq) ]
iv. Substitute values to the working equation:
0.0591 v
E = +1.05 v − log(0.8) = + 1.0528 V
2

37
PRACTICE EXERCISE 2.2
1. Use the Nernst equation to calculate the cell potentials of the following cells
at 298 K:
a. Cu(s) + PtCl62-(aq)(0.10 M) → Cu2+(aq)(0.20 M) + PtCl42-(aq)(0.10 M) +
2Cl-(aq)(0.40 M)
b. Pb(s) + SO4 (aq)(0.30M) + 2AgCl(s) → PbSO4(s) + 2Ag(s) + 2Cl-(aq)(0.20M)
2-

2. One half-cell in a voltaic cell is constructed from a silver wire dipped into a
AgNO3 solution of unknown concentration. The other half-cell consists of a
zinc electrode in a 1.0 M solution of Zn(NO3)2. A potential of 1.48 V is
measured for this cell. Use this information to calculate the concentration
of Ag+(aq).

2.4 Significance of Electromotive Force

Electromotive force is used to calculate the amount of electrical energy,
equilibrium constant (K) and standard free-energy change (ΔG0). The K and
ΔG0 are also used to determine the spontaneity of the redox reaction.
ΔG0 K Spontaneity of the reaction Direction of the reaction
Negative >1 Spontaneous reaction Favors forward reaction
0 =1 No net change At equilibrium
Positive <1 Non-spontaneous reaction Favors reverse reaction

2.4.1 Amount of electrical energy

The constant flow of electrons generates electrical energy. Electrical energy
is the product of electromotive force expressed in volts and the total electrical
charge in coulombs, which is equal to the number of moles of electrons (n) that
pass through the circuit multiplied to the Faraday’s constant, F .
Electrical energy=nF x E0
= mol e- (C/mol e-) x volts
= coulombs x volts
= joules
Hence:
96500 J
1J = 1 C X 1 V 1 F = V ∙ mol e−
Thus, the amount of electrical energy generated by the reaction:
Zn(s) + Cu+2(aq) → Zn+2(aq) + Cu(s) with E0 = +1.10 V is
Electrical energy = nF x E0cell

38
 = (2 mol)(96500 coulomb/mol)(1.10 V)
Electrical energy = 2.12 x 105 C∙ V or 2.12 x 105 Joules

2.4.2. Free- energy change (ΔG0)

Electromotive force (E0) and free-energy change at standard-state
conditions are related as can be seen below:
ΔG0 = - nFE0cell
The change in free energy is the maximum amount of useful electrical work
that can be obtained from the reaction. The (-) sign implies that electrical work is
done on the surroundings.
For the reaction written above, free-energy change is:
ΔG0 = - nFE0cell
ΔG0 = - (2)(96500 coulomb/mol)(1.10 V)
ΔG0 = - 2.12 x 105 coulomb∙V/mol = - 2.12 x 105 J/mol

2.4.3. Equilibrium Constant (K)

Free-energy change is written as: ΔG0 = - RT ln K

Therefore, it can also be written as: - nFE0cell = - RT ln K
Deriving K:
0
nF Ecell
ln K =
RT
Using R = 8.314 J/K∙mol,
F = 96500 J/V ∙mol, and
T = 298 K
J 0
n (96500 ∙ mol) Ecell
ln K = V
J
(8.314 K ∙ mol) 298 K
0
n Ecell
ln K =
0.0257 V
If a= n E0cell/0.0257 V, hence
K = ea
Again, for the reaction: Zn(s) + Cu+2(aq) → Zn+2(aq) + Cu, equilibrium constant
is:
0
𝑛 𝐸𝑐𝑒𝑙𝑙
ln 𝐾 =
0.0257 𝑉

2 (1.10 𝑉)
ln 𝐾 =
0.0257 𝑉

ln 𝐾 = 85.6
K = 1.50 𝑥 1037

39
 PRACTICE EXERCISE 2.3
Calculate the (a) electrical energy, (b) ΔG0, and (c) K of the reaction:
1. Fe+2(aq) / Fe+3(aq) // Ag+(aq) / Ag(s)
2. Zn(s) / Zn+2(aq) // Cr+3(aq) / Cr(s)
3. Fe(s) + Hg+2(aq) ---> Fe+2(aq) + Hg(l)
4. Zn(s) + Ni+2(aq) → Zn+2(aq) + Ni(s)
5. Pb(s) + Sn+2(aq) → Pb+2(aq) + Sn(s)
6. Al(s) / Al+3(aq) // Mg+2(aq) / Mg(s)
7. Ca(s) / Ca+2(aq) // Cr+3(aq) / Cr(s)
8. Mg(s) / Mg+2(aq) // Fe+2(aq) / Fe(s)

2.5 Applications of Oxidation-Reduction Reactions

2.5.1 Batteries- these include primary cells like dry cells, and secondary cells such
as lead storage battery and Edison storage battery. Primary cells or
irreversible cells cannot be recharged because the electrodes and
electrolytes cannot be restored to the original state by an external potential.
On the other hand, secondary cells can be used repeatedly. The
substances used in the production of electricity through cells are in the
reverse direction during discharge. This recharges the cell. Examples of
secondary cells are lead storage battery, Edison storage battery and nickel-
cadmium storage cell.

The Dry Cell

a. Carbon-Zinc dry cell
The Main Components:
1. Zn-anode
2. Carbon rod-cathode
3. Paste of MnO2, NH4Cl, H2O as
the electrolyte
4. Porous paper- separates the
paste from the Zn casing, also
allows for the diffusion of ion.

Figure 2.2: Dry Cell (Voltage output=

1.5V)

40
The reactions involved are:
Anode: Zn(s) → Zn+2(aq) + 2e-
Cathode: 2 NH4+1 (aq) + 2MnO2(s) + 2e- → Mn2O3(s) + 2NH3(aq) + H2O (l)
Over-all Zn(s) + 2NH4+1 (aq) + 2MnO2(s) → Zn+2(aq) + Mn2O3(s) + 2NH3(aq) + H2O (l)

The cathode reaction is complex and a mixture of products is formed.

As NH3 builds up around the carbon rod, it insulates the rod thus
decreasing the power output, but when the cell is allowed to rest, the
NH3 diffuses towards the anode and combines with Zn+2 ions.

b. Alkaline cell also uses Zn and MnO2 but KOH is the electrolyte. The
voltage output is about 1.54 V. It has a longer shelf-life and delivers
higher currents for longer period than Zn-C cell. Alkaline cell is often sold
as cheap watch battery. It is also the battery used in flashlights, MP3
players, and handheld video games.
Anode: Zn + 2 OH- → ZnO + H2O + 2e-
2MnO2 + H2O + 2e-→ Mn2O3 + 2OH-
Cathode:
Zn + 2MnO2 → ZnO + Mn2O3

c. Mercury cell can be made compact so it is used where small size is

important like in pacemakers, hearing aids and electric watches. The
electrolyte is KOH.
Anode: Zn + 2 OH- → ZnO + H2O + 2e-
Cathode: HgO + H2O + 2e-→ Hg + 2OH-
Zn + HgO → ZnO + Hg
The Hg does not flow since it is mixed with HgO and graphite powder.
The electrolyte is held by an absorbent cotton pad. The emf is 1.3 V.

d. Silver oxide cell is the miniature battery used in wristwatches,

calculators and autoexposure cameras. The silver content increases the
cost of the cell. The emf is about 1.5 V.

Anode: Zn + 2 OH- → Zn(OH)2 + 2e-

Cathode: Ag2O + H2O + 2e-→ 2Ag + 2OH-
Zn + Ag2O + H2O → Zn+2 + 2 OH- + 2Ag or
Zn + Ag2O + H2O → Zn(OH)2 + 2 Ag

41
Secondary cells
a. Lead Storage Battery
The lead storage battery functions as a voltaic cell when used as a
source of direct current e.g. to start the engine of a vehicle or to supply
power to the electrical accessories of the vehicle. When the engine is
running, it functions as an electrolytic cell.
The components are (a) Pb spongy as anode (b) PbO2 and (c) dilute
aqueous solution of H2SO4.
When the cell is discharging the reactions are:
Anode: Pb(s) + SO42- (aq) → PbSO4(s) + 2e-
Cathode: PbO2(s) + 4H+(aq) + SO42- (aq) + 2e- → PbSO4(s) + 2H2O (l)
Over-all Pb(s) + PbO2(s) + 4H+(aq) + 2SO42- (aq) → 2PbSO4(s) + 2H2O (l)

The PbSO4 is insoluble in water and sticks to both electrodes and

causes the discharging of batteries. The electrolyte is also depleted of the
H2SO4 and the concentration decreases, whereby the density also
decreases. The density indicates the state of charge of the battery.
Running an external current recharges the battery, the flow of electrons
and the chemical reactions at each electrode can be reversed.
Anode: PbSO4(s) + 2H2O (l) → PbO2(s) + 4H+(aq) + SO42- (aq) + 2e-
Cathode: PbSO4(s) + 2e- → Pb(s) + SO42- (aq)
Over-all: 2PbSO4(s) + 2H2O (l) → Pb(s) + SO42- (aq) + PbO2(s) + 4H+(aq) + 2SO42- (aq)

The heat produced during the discharging can evaporate some of

the water from the cells. Distilled water should be used to restore the fluid
back. Impurities in water may cause the loss of charge on a battery.

b. Edison storage battery

The Edison storage battery consists of steel anode plates packed with
iron and cathode plates packed with hydrated NiO2. The electrolyte is
21% KOH solution with some LiOH. When the cell is delivering current,
the reactions are:
Anode: Fe → Fe2+ + 2e-
Cathode: 2H2O +NiO2 + 2e-→ Ni2+ + 4OH-
Over-all reaction: Fe + 2H2O +NiO2→ Fe2+ + Ni2+ + 4OH- or
Fe + 2H2O +NiO2 → Fe2+ + Ni(OH)2 + 2OH-
The emf of each cell is about 1.47 V. The battery is sealed otherwise
the KOH and the LiOH will form carbonates with atmospheric CO 2. The
edison storage battery is lighter and more durable than the lead storage
battery, but it is more expensive.

42
 c. Nickel-Cadmium storage cell
The Nickel-Cadmium storage cell is the battery that powers
rechargeable electronic calculators, electric shavers and power rods.
The emf of the cell is about 1.4 V.
Anode: Cd + 2 OH- → Cd(OH)2 + 2e-
Cathode: NiO2 + 2H2O + 2e-→ Ni(OH)2 + 2OH-
Cd + NiO2 + 2H2O → Cd(OH)2 + Ni(OH)2

d. Hydrogen Fuel Cells

In this cell, hydrogen and oxygen gases are bubbled through the two
inert electrodes to form water, heat, and electricity. The anode-cathode
reactions are:
Anode: 2H2(g) + 4OH-(aq) → 4H2O (l) + 4e-
Cathode: O2(g) + 2H2O(l) + 4e- → 4OH- (aq)
Over-all 2H2(g) + O2(g) → 2H2O (l)

2.5.3 Corrosion
Corrosion is the chemical attack on the metal or deterioration of metal
through oxidation by its environment. It is a galvanic process wherein the metal
that corrode acts as the anode.
In the rusting of iron, the following steps occur:
1. Fe + 2H2CO3 → Fe+2 + 2H+ + 2HCO3- + 2e-
2. 4H+ + O2 + 4e- → 2H2O
3. 4Fe+2 + O2 + (4 + 2x) H2O → 2Fe2O3•XH2O + 8H+

2.6 Electrolysis
Electrolysis is a process that utilizes electrical potential energy to cause a
chemical reaction that does not occur spontaneously. As direct current is passed
through a solution of an electrolyte, the anions move towards the anode, where
they give up their electrons. The electrons move through the metallic conductor
and through the generator of the electric current to the cathode, where the cations
are discharged by taking up these electrons.

2.6.1. Electrode Products

It is not always easy or even possible to predict what products will result
when a direct current is passed through an aqueous solution of an electrolyte. In
addition to the ions from the electrolyte, water molecules and the ions from
water(H+ and OH-) are present. These may also participate in the electrochemical
reactions. Furthermore, the electrode products obtained with concentrated

43
solutions (or molten state) often differ from those obtained with dilute solutions. In
some cases, one or both of the electrodes may react (the anode in the
electroplating of silver is one of the reactants). To narrow the list of variables, inert
electrodes, usually platinum, are used. The following rules are applied to predict
electrode products for a considerable number of reactants.

At the inert cathode (-), the following occurs,

1. If the metal is below hydrogen activity, electrolysis of aqueous solution of
its salts causes the metal to form at the cathode. For example, if a water
solution of CuCl2, of AgNO3 or of HgCl2 is electrolyzed, Cu, Ag, or Hg,
respectively will be formed.
2. If a metal is above hydrogen in activity, electrolysis of aqueous solutions
of it usually liberates hydrogen gas at the cathode. For example, if
aqueous NaCl, or KCl, or MgCl2 is electrolyzed, hydrogen will be liberated
at the cathode in each case.

At the inert anode (+), the following occurs,

1. Oxygen is liberated during the electrolysis of most salts with anions
containing oxygen, such as SO4-2 and NO3-. Example:
4 AgNO3 + 2 H2O 4 Ag + O2 + 4 HNO3

2H2O O2 + 4H+ + 4e- (anode)

2. Anions such as Cl -, Br -, and I – (but not F-) are more easily oxidized than
water. Hence, the free halogen is liberated. For example, during
electrolysis of molten or concentrated sodium chloride, chlorine is liberated
at the anode. In case of dilute solution, oxygen as well as chlorine are
formed.

(a) (b)
Anode Rxn: 2Cl- → Cl2 + 2e- A.R: 2O-2 → O2 + 4e-
Cathode Rxn: Na+ + 2e- → Na 2Cl- → Cl2 + 2e-
C.R: 2H+ + 2e- → H2
Figure 2.3: Schematic representation of the electrolysis of (a) molten NaCl
and (b) aqueous solution of NaCl.

44
 EXAMPLE
Predict what is liberated at each electrode when each of the following
electrolytes is electrolyzed between inert electrodes.

Electrolytes Cathode Product Anode Product

1. molten AlCl3 Al Cl2
2. dilute solution of AlCl3 H2 Cl2, O2
3. aqueous solution of Mg(NO3)2 H2 O2
4. aqueous solution of CuSO4 Cu O2
5. concentrated solution of CuCl2 Cu Cl2

PRACTICE EXERCISE 2.3

1. Explain why different products are obtained in the electrolysis of
molten ZnCl2 and in the electrolysis of an aqueous solution of ZnCl2.

2. What is liberated at each electrode when the following are

electrolyzed between inert electrodes?
a. Aqueous solution of Na3PO4
b. Molten KCl
c. Aqueous solution of AgNO3
d. Concentrated solution of NiSO4
e. Dilute solution of AuCl3

2.7 Application of Electrolysis

Electrolysis with active electrodes has a number of industrial applications
among which are electroplating, the production of some common chemicals like
aluminum, magnesium, and sodium, the refining of copper and the synthesis of
sodium hydroxide and sodium hypochlorite.

A. Electroplating
Electroplating is the process of coating a material with metals to improve
its appearance and durability. For example, bumpers are chrome-plated to
make them attractive and to prevent rusting of steel. Likewise, silver or gold
plating is applied to less expensive jewelry to make it lustrous and beautiful.

45
 In electroplating, the plating metal is the anode while the article to be plated
is the cathode. Both electrodes are immersed in the plating bath which is an
aqueous solution of a salt of the plating metal. For example, in copper plating,
the solution may be made from CuSO4; for silver plating, AgNO3. The current
source is DC and in commercial production, a rectifier is used to convert the
AC to DC.

The figure at the right shows

the set-up for electroplating silver.
The Ag+ ion from the solution is
reduced at the cathode where it is
deposited as metallic Ag. The Ag
atom from the plating metal is
oxidized and the Ag+ goes into the
solution to replace the used up
Anode: Cathode:
ions. Ag → Ag+ + e- Ag+ + e- → Ag
Figure 2.4: Electroplating Set-up

B. Production of Aluminum
The Hall Process produces aluminum by electrolysis. The ore, bauxite,
contains Al2O3. After the ore is purified the Al2O3 is added to molten cryolite,
Na3AlF6, which is the electrolyte. The Al2O3 dissolves and dissociates. These
reactions at the electrodes are:
Cathode: [Al+3 + 3e- → Al (s)] x 4 4Al+3 + 12e- → 4Al(s)
Anode: [2 O-2 → O2(g) + 4e-] x 3 6 O-2 → 3O2(g) + 12e-
4Al+3 + 6 O-2 → 4Al(s) + 3O2(g)
The aluminum forms as a layer below the less dense electrolyte. The oxygen
attacks that carbon anode producing CO2 so that the anode is replaced
frequently and such together with the enormous amount of electricity consumed
add to the cost of production.

C. Production of Magnesium
The seawater, which is the major source of Mg, is made basic to precipitate
the Mg(OH)2 which is separated by filtration. Adding HCl produce MgCl2 which
is melted and electrolyzed.
Cathode: Mg+2 + 2e- → Mg(s)
Anode: 2 Cl- → Cl2(g) + 2e-
Mg+2 + 2Cl- → Mg(s) + Cl2(g)

46
D. Purification of Copper
The impurities in copper mostly Ag, Au, Pt, Fe, and Zn reduce its electrical
conductivity. In the refining of copper, the anode is the impure copper and the
cathode is a thin sheet of very pure copper. The electrolyte is a solution of
CuSO4 in H2SO4. Under correct voltage only the Cu and the impurities more
easily oxidized than Cu (like Zn and Fe) dissolve at the anode. The less active
metals simply settle at the bottom of the container. At the cathode, only the
Cu+2 ions are reduced, but the Zn and Fe ions remain in solution because they
are more difficult to reduce than Cu. Gradually the impure Cu dissolves and
the pure Cu cathode grows. The sludge called anode mud accumulates and is
removed periodically and this is a good source of the precious metals, Ag and
Au.

CuSO4/H2SO4 anode mud

electrolyte
Figure 2.5: Purification of Copper by Electrolysis

Quantitative Changes During Electrolysis

Faraday from his series of experiments arrived at the quantitative relationships
between the amount of chemical changes during electrolysis and the quantity of
current used and the length of time the process is run.
1. The mass of the chemical substances produced at the electrode is directly
proportional to the electricity passed through the solution. Consider the
following cathode reactions:
a. Ag+ + 1e- → Ag 1 mole of electrons (6.02 x 1023) deposits
1 mole Ag (108 g)
b. Cu + 2e → Cu
+2 - 2 moles of electrons deposit 1 mole Cu (64g)
or 1 mole of electrons deposit ½ mole Cu
c. Au+3 + 3e- → Au 3 moles of electrons deposit 1 mole Au
(197g) or 1 mole of electrons deposits 1/3
mole Au
If the amount of the metal that receives 1 mole of electrons (which is also
equal to 1 Faraday) is equal to the equivalent mass of the element then a
current of 1 Faraday will cause the oxidation or reduction of 1 equivalent
mass of the substances.
47
 2. The masses of the different substances produced by the same quantity of
electricity are proportional to their equivalent masses.
When two different metals are deposited by the same amount of
electricity and the same time, more of the metal with higher equivalent mass
will be deposited. With the same amount of electricity and with the same
time, more Ag will be deposited (EM = 108 g/eq) compared with Cu (EM =
32 g/eq).

Calculations Involving Faraday’s Law of Electrolysis

The following equivalents may be used in the calculations:
1 mole electrons (6.02 x 1023) = 1 Faraday
1 Faraday = 96,500 coulombs
Ampere = coulomb/second
amount deposited
ECE =
coulomb
EM
ECE =
96,500 coulomb/F
where ECE = Electrochemical Equivalent
EM = Equivalent Mass
MM
and EM =
no.of e−transferred

EXAMPLES
1. How many grams of Ag will be deposited at the cathode if a current of 5.0
A is passed through a Ag plating cell for 45 seconds?
Solution:
108
( )g/eq
1
ECE of Ag = = 0.00111 g/coulomb
96,500 coulomb/eq
Amount deposited = ECE x I x t
0.00111 g
Amount deposited = x 5 A x 45 s = 0.25 g Ag
coulomb

2. How many minutes will be required to run a current of 2.0 A in CuSO 4

solution to deposit 0.80 grams of Cu?
Solution:
Cathode: Cu+2 + 2e- → Cu
Amount deposited = 0.80 grams Cu
Current, I = 2.0 A
g eq
(64 )/ (2 )
mole mole
ECE = = 3.3 x 10-4 g/coulomb
96,500 coulomb/eq

48
 time , t = ? in minutes
amount deposited = ECE x I x t
amount deposited 0.80 g
t = =
ECE x I (3.3 x 10−4 g/coulomb)x 2.0A
1 min
t = 1,212.12 s x = 20 min
60 s

PRACTICE EXERCISE 2.4

1. A steady current of 3 A is maintained for 10 minutes in a AgNO3 solution.
How much Ag is deposited at the cathode?
2. How long will it take to deposit 1.5 g of Cu on a metal when a current of
5 A is applied to a CuSO4 solution?
3. What current strength in ampere is required to deposit 500 mg of Ni from
a Ni+2 plating cell for an hour?
4. How many coulomb will it take to plate out 11.2 g of Fe from a solution
of FeCl2?
5. In a NiSO4 bath, a current of 12 A is employed to plate Ni on both sides
of the cathode, a square metal sheet, 5 cm on each side. The density
of the metal is 10.5 g/cm3.
a. How much Ni is plated on the cathode in one hour?
b. What is the thickness of the plating on the cathode?
6. Considering only the cost of electricity, would it be cheaper to produce
a ton of sodium or a ton of aluminum by electrolysis?

49
Name: _______________________________ Date: ____________________
Course/Year/Section: ___________________

EXERCISE 2.1
Electrode Potentials and Voltaic Cells

1. Predict whether the following reactions would occur spontaneously in

aqueous solution at 25oC. Assume that the initial concentration of dissolved
species are all 1.00M.
a. Ca(s) + Cu+2(aq) → Cu(s) + Ca+2(aq)
b. 2 Br-(aq) + Sn+2(aq) → Br2(l) + Sn(s)
c. 2 Ag(s) + Ni+2(aq) → 2 Ag+(aq) + Ni(s)

2. For the cell notation Mg / Mg+2 // Sn+2 / Sn.

a. What is Eo for the cell?
b. Write the chemical equation for the cell reaction.
c. Which electrode is positive?

3. For the cell U / U+3 // Ag+ / Ag Eo = 2.588 V

Use the emf of the cell and E for Ag+ / Ag couple to calculate for the U+3 /
o

U half-cell reaction.

4. Consider a voltaic cell consisting of a magnesium electrode in contact with

1.0 M Mg(NO3)2 and a cadmium electrode in contact with 1.0 M Cd(NO 3)2.
Calculate Eo for the cell and draw a diagram showing the cathode, the
anode, and the direction of electron flow.

50
Name: _______________________________ Date: ____________________
Course/Year/Section: ___________________

EXERCISE 2.2
Nerst Equation

Predict whether the reaction is spontaneous at 298 K.

a. Mg(s) + Fe+2 (aq) →Mg+2(aq) + Fe(s)

Fe+2 (aq) = 0.18 M
Mg+2 (aq) = 0.53 M

b. Cd(s) + Sn+2(aq) →Cd+2(aq) + Sn(s)

Sn+2(aq) = 0.69 M
Cd+2(aq) = 0.08 M

c. Zn (s) + Ni+2(aq) → Zn+2(aq) + Ni(s)

Ni+2 (aq) = 0.50 M
Zn+2 (aq) = 0.76 M

d. Cu+2(aq) + Sn(s) →Cu(s) + Sn+2(aq)

Cu+2(aq) = 0.12 M
Sn+2 (aq) = 0.030 M

51
Name: _______________________________ Date: ____________________
Course/Year/Section: ___________________

EXERCISE 2.3
Electrolyis

1. Predict what is liberated at each electrode when aqueous solution of the

following are electrolyzed between inert electrodes.

Anode Product Cathode Product

a. H2SO4

b. K2SO4

c. CuSO4

d. AuCl3

e. KCl

2. Calculate the amounts of Cu and Br2 produced at the inert electrodes by

passing a current of 4.5 A through a solution of CuBr2 for 1.0 hr.

3. In the electrolysis of an aqueous AgNO3 solution, 0.67 g of Ag is deposited

after a certain period of time.
a. Write the half-reaction for the reduction of Ag+.
b. What is the probable oxidation half-reaction?
c. Calculate the quantity of electricity used, in coulomb.

4. A steady current was passed through molten CoSO4 until 2.35 g of metallic
cobalt was produced. Calculate the number of coulombs of electricity used.

5. A quantity of 0.300 g of copper was developed from a CuSO 4 solution by

passing a current of 3.00 A for 304 s. Calculate the value of the Faraday
constant.

52
53