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
SY: 2020 - 2021
2
CHEM ENG
MODULE 1: ELECTROCHEMISTRY

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.
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
SY: 2020 - 2021
3
CHEM ENG
MODULE 1: ELECTROCHEMISTRY

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.

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
SY: 2020 - 2021
4
CHEM ENG
MODULE 1: ELECTROCHEMISTRY

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?

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
SY: 2020 - 2021
5
CHEM ENG
MODULE 1: ELECTROCHEMISTRY

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

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
SY: 2020 - 2021
6
CHEM ENG
MODULE 1: ELECTROCHEMISTRY

ions, the positive ions towards the CuSO4 and the negative ions towards the
ZnSO4.
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
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
SY: 2020 - 2021
7
CHEM ENG
MODULE 1: ELECTROCHEMISTRY

metal. Therefore, less active metal has greater tendency to be reduced, and more
active metal has greater tendency to be oxidized.
Table 1.1. 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) + SO4-2 (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

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
SY: 2020 - 2021
8
CHEM ENG
MODULE 1: ELECTROCHEMISTRY

K+ (aq) + e- → K(s) -2.93

Li+ (aq) + e- → Li(s) -3.05

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

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
SY: 2020 - 2021
9
CHEM ENG
MODULE 1: ELECTROCHEMISTRY

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

positive, the reaction is spontaneous.

(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).

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
SY: 2020 - 2021
10
CHEM ENG
MODULE 1: ELECTROCHEMISTRY

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)?

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
SY: 2020 - 2021
11