Module 1 - Electrochemistry

CHEM ENG
MODULE 1
ELECTROCHEMISTRY
prepared by
• Silfavan • Rodil • Capinding

• Sacdalan • Cabildo • Ergino
Chemistry Department
College of Science
Technological University of the Philippines, Manila
SY 2020 – 2021
CHEM ENG
MODULE 1: ELECTROCHEMISTRY
OVERVIEW:
In this module, you will study the theoretical aspects and other applications
of electrochemical reactions. The discussions begin with a review of redox reactions
and where you will learn how to balance equations describing these processes.
(Lesson 1.1)
Next, you will examine the essentials of voltaic cells. Here you will learn to
determine the standard reduction potentials based on the standard hydrogen
electrode reference and use them to calculate the emf of a cell and hence the
spontaneity of a cell reaction. (Lesson 1.2 – 1.3)
Consequently, you will learn to calculate the emf of a cell under nonstandard
conditions using the Nernst equation. (Lesson 1.4)
Then you will see that a significant relationship exists between an emf of a
cell, the change in the standard Gibb’s free energy and the equilibrium constant for
the cell reaction. (Lesson 1.5)
Moreover, you will examine the application of oxidation – reduction reactions

in several common types of batteries, the operation of fuel cells, and in the corrosion
of metals. (Lesson1.6)
Finally, you will explore a nonspontaneous electrochemical process—

electrolysis and learn the quantitative aspects of electrolytic processes and its
applications. (Lesson 1.7 – 1.8)
Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO

Chemistry Dept. / COS, TUP Manila
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CHEM ENG
OBJECTIVES:
At the end of this module, you should be able to:
1. explain the concept of electrochemistry;
2. use the terminology of electrochemistry (terms such as “cell,” “electrode,”
“cathode,” “anode”);
3. differentiate the types of electrochemical cells;
4. recognize oxidation and reduction half-reactions, and know at which
electrode each occurs;
5. describe the construction of simple voltaic cells from half-cells and a salt
bridge, and understand the function of each component;
6. write half-reactions and overall cell reactions for voltaic cells;
7. compare various voltaic cells to determine the relative strengths of
oxidizing and reducing agents;
8. interpret standard reduction potentials;
9. use standard reduction potentials, E0, to calculate the potential of a
standard voltaic cell, E0 cell;
10. use standard reduction potentials to identify the cathode and the anode
in a standard cell;
11. use standard reduction potentials to predict the spontaneity of a redox
reaction;
12. use standard reduction potentials to identify oxidizing and reducing
agents in a cell or in a redox reaction;
13. Use the Nernst equation to relate electrode potentials and cell potentials
to different concentrations and partial pressures;
14. Relate the standard cell potential (E0 cell) to the standard Gibbs free
energy change (ΔG0) and the equilibrium constant (K);
15. Distinguish between primary and secondary voltaic cells
16. distinguish between primary and secondary voltaic cells;
17. describe the compositions and reactions of some useful primary and
secondary cells (batteries);
18. describe the electrochemical processes involved in discharging and
recharging a lead storage (automobile) battery;
19. Describe some corrosion processes and some methods for preventing
corrosion;
20. predict electrode products of a given electrolysis process;
21. write half-reactions and overall cell reactions for electrolysis processes;
22. explain Faraday’s Law of electrolysis;
23. solve problems on Faraday’s Law as applied to electroplating;
24. describe the refining and plating of metals by electrolytic methods; and
25. give some applications of electrolysis.
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CHEM ENG
LESSON 1.1 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.

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CHEM ENG
Practice Task 1.1:
Consider the following balanced redox reaction:

3H2SO4(aq) + 2KMnO4(aq) + 10HCl(aq) → 2Mn2SO4(aq) + K2SO4(aq) + 5Cl2(g) + 8H2O(l)
(a) Which species is being oxidized?
(b) Which species is being reduced?
(c) Which species is the oxidizing agent?
(d) Which species is the reducing agent?
(e) From which species to which does electron transfer occur?

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CHEM ENG
LESSON 1.2 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 1.1: 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.
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CHEM ENG
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.
LESSON 1.3 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 3.1:
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.
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CHEM ENG
Table 1.1. Standard Reduction Potentials in Aqueous Solution (1M) at 25 0C
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) + SO4-2 (aq) + 2e- → PbSO4(s) + 2H2O +1.70
MnO4-(aq) +8H+(aq) + 5e- → Mn+2(aq) + 4H2O +1.51
Stronger Weaker
oxidizing Au3+ (aq) + 3e- → Au(s) +1.50 reducing
agent Cl2(g) +2e- →2Cl- (aq) +1.33 agent
MnO2 (aq) +4H+(aq) + 2e- → Mn+2(aq) + 2H2O +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
Ag1+ (aq) + e- → Ag(s) +0.80
Fe3+ (aq) + e- → Fe2+(aq) +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
Cu2+ (aq) + 2e- → Cu(s) +0.34
SO42-(aq) +4H+(aq) +2e- →SO2(g) +2H2O +0.20
2H+ (aq) + 2e- → H2(g) 0.00
Pb2+ (aq) + 2e- → Pb(s) -0.13
Sn2+ (aq) + 2e- → Sn(s) -0.14
Ni2+ (aq) + 2e- → Ni(s) -0.25
Co2+ (aq) + 2e- → Co(s) -0.28
PbSO4(s) +2e- →Pb(s) +SO42-(aq) -0.31
Cd2+ (aq) + 2e- → Cd(s) -0.40
Weaker Fe2+ (aq) + 2e- → Fe(s) -0.44 Stronger
oxidizing Cr3+ (aq) + 3e- → Cr(s) -0.74 reducing
agent Zn2+ (aq) + 2e- → Zn(s) -0.76 agent
2H2O + 2e- → H2(g) +2OH-(aq) -0.83
Mn2+ (aq) + 2e- → Mn(s) -1.18
Al3+ (aq) + 3e- → Al(s) -1.66
Mg2+ (aq) + 2e- →Mg(s) -2.37
Na+ (aq) + e- → Na(s) -2.71
Ca2+ (aq) + 2e- → Ca(s) -2.87
Ba2+ (aq) + 2e- → Ba(s) -2.90
K+ (aq) + e- → K(s) -2.93
Li+ (aq) + e- → Li(s) -3.05
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CHEM ENG
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 E 0 is

positive, the reaction is spontaneous.

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CHEM ENG
(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).

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CHEM ENG
Practice Task 1.2:
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)?

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CHEM ENG
LESSON 1.4 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
J
F – Faraday constant, 1 F = 96500
V ∙ mol e−
n – the number of electrons transferred in the redox reaction, mol e - /mole rxn
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
𝐹
Thus the equation becomes

0.0591 𝑉
E = 𝐸0 − log 𝑄
𝑛
or
0.0591 𝑉
𝑛
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CHEM ENG
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
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 = 2 mol e- / mole rxn
[Zn+2
(aq) ] [0.40]
iv. Keq = = = 83.33
[Cu+2
(aq) ] [4.8𝑥10−3 ]
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 = 2 mol e- / mole rxn

[Ni+2
(aq) ] [0.20]
iii. Keq = = = 0.8
[Ag+1
(aq) ]
2 [0.5]2
iv. Substitute values to the working equation:
0.0591 v
E = +1.05 v − log(0.8) = + 1.0528 V
2
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CHEM ENG
Practice Task 1.3:
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) + SO42-(aq)(0.30M) + 2AgCl(s) → PbSO4(s) + 2Ag(s) + 2Cl-
(aq)(0.20M)
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).

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CHEM ENG
LESSON 1.5 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
1.5.1 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- / mole rxn (C/mol e-) x volts
= coulombs/mole rxn x volts
= joules/ mole rxn
Hence:
J coulomb
1J = 1 C X 1 V 1 F = 96500 = 96500
V ∙ mol e− 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
= (2 mol e- /mole rxn)(96500 coulomb/mol e-)(1.10 V)
Electrical energy = 2.12 x 105 C∙ V or 2.12 x 105 Joules/mole rxn
1.5.2 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.
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CHEM ENG
For the reaction written above, free-energy change is:

ΔG0 = - nFE0cell
ΔG0 = - (2mol e-/mole rxn)(96500 coulomb/mol e-)(1.10 V)
ΔG0 = - 2.12 x 105 coulomb∙V/mole rxn = - 2.12 x 105 J/mole rxn
1.5.3 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 e-, and
T = 298 K
n = mol e- /mole
J 0
n (96500 − ) Ecell
ln K = V mol 𝑒
J
(8.314 ) 298 K
K • mole
0
n Ecell
ln K =
0.0257 V
n E0cell
If a = , hence, K = ea
0.0257 V
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

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CHEM ENG
Practice Task 1.4:
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)

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CHEM ENG
LESSON 1.6 Applications of Oxidation – Reduction Reactions

1.6.1 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 1.2: Dry Cell (Voltage output=1.5V)

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-
Cathode: 2MnO2 + H2O + 2e-→ Mn2O3 + 2OH-
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.
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CHEM ENG
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 auto exposure 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
The 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) PbO 2 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.
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CHEM ENG
b. Edison storage battery

The Edison storage battery consists of steel anode plates packed with
iron and cathode plates packed with hydrated NiO 2. 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.
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)
1.6.2 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+

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CHEM ENG
LESSON 1.7 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.
1.7.1 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 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

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CHEM ENG
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: 2H2O → O2 + 4H+ + 4e-
Cathode Rxn: 2Na+ + 2e- → 2Na 2Cl- → Cl2 + 2e-
C.R: 6H+ + 6e- → 3H2
Figure 1.3: Schematic representation of the electrolysis of (a) molten NaCl
and (b) aqueous solution of NaCl.
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

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CHEM ENG
Practice Task 1.5:
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

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CHEM ENG
1.7.2 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+2 + 2e- → Cu 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.
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
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CHEM ENG
where ECE = Electrochemical Equivalent

EM = Equivalent Mass
MM
and EM =
no.of e−transferred
MM = molar mass
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
( 1 )g/mol 𝑒 −
ECE of Ag = = 0.00111 g/coulomb
96,500 coulomb/mol 𝑒 −
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 CuSO4

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 mol 𝑒−
(64mole)/ (2 mole )
ECE = = 3.3 x 10-4 g/coulomb
96,500 coulomb/mol 𝑒 −
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

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CHEM ENG
Practice Task 1.6:
1. A steady current of 3 A is maintained for 10 minutes in a AgNO 3 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?

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CHEM ENG
LESSON 1.8 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.
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 1.4: 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)
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CHEM ENG
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)
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 1.5: Purification of Copper by Electrolysis

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CHEM ENG
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 Eo for Ag+ / Ag couple to calculate for the U+3 / 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.

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CHEM ENG
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

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CHEM ENG
Electrolysis
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.

SY: 2020 - 2021
31

Module 1 - Electrochemistry

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Module 1 - Electrochemistry

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CHEM ENG

• Silfavan • Rodil • Capinding

Moreover, you will examine the application of oxidation – reduction reactions

Finally, you will explore a nonspontaneous electrochemical process—

Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO

LESSON 1.1 Electrochemical Reactions

Examples of electrochemical reaction:

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

Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO

Practice Task 1.1:

Consider the following balanced redox reaction:

(a) Which species is being oxidized?

(b) Which species is being reduced?

(c) Which species is the oxidizing agent?

(d) Which species is the reducing agent?

(e) From which species to which does electron transfer occur?

Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO

LESSON 1.2 Voltaic Cells

Figure 1.1: Daniel Cell

In the Daniel Cell:

6. The over-all reaction is as follows:

LESSON 1.3 Electrode Potential

Table 1.1. Standard Reduction Potentials in Aqueous Solution (1M) at 25 0C

For each of the following:

(1) Zn(s) + Cu+2(aq) → Zn+2(aq) + Cu(s)

Since Zn which is more active than Cu is placed in the anode and E 0 is

Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO

(2) Al(s) + Mg+2(aq) → Al+3(aq) + Mg(s)

anode (oxidation): 2Al(s) → 2Al+3(aq) + 6e- E0 = + 1.66 V

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

To make the reaction spontaneous, Mg must be in the anode (must undergo

Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO

Practice Task 1.2:

I. For each of the following;

2. Pb(s) + Sn+2(aq) → Pb+2(aq) + Sn(s)

Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO

LESSON 1.4 Nonstandard Conditions

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

Thus the equation becomes

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

i. anode (oxidation): Ni(s) → Ni+2(aq) + 2e- E0 = + 0.25 V

ii. n = 2 mol e- / mole rxn

Practice Task 1.3:

Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO

LESSON 1.5 Significance of Electromotive Force

1.5.1 Amount of Electrical Energy

1.5.2 Free – Energy Change (ΔG0)

For the reaction written above, free-energy change is:

1.5.3 Equilibrium Constant (K)

Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO

Practice Task 1.4:

Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO

LESSON 1.6 Applications of Oxidation – Reduction Reactions

Figure 1.2: Dry Cell (Voltage output=1.5V)

Anode: Zn + 2 OH- → ZnO + H2O + 2e-

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

The Secondary cells

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

Anode: PbSO4(s) + 2H2O (l) → PbO2(s) + 4H+(aq) + SO42- (aq) + 2e-

b. Edison storage battery

c. Nickel-Cadmium storage cell

d. Hydrogen Fuel Cells

Prepared by: E. V. SILFAVAN•C.D.SACDALAN•M.S.P.RODIL•M.C.T.CABILDO•E.S.CAPINDING•G.A.ERGINO