Redox Reactions

What are oxidation-reduction reactions? When is a

reaction a reduction reaction? When is it an oxidation Section Objectives
reaction?
At the end of this section, you
A type of chemical change where electron transfer should be able to
occurs is classified as an oxidation-reduction (redox)
1. recognize oxidation
process. The ability of the electrons to be transferred from
and reduction reactions; and
one species to another is dependent on the species' reduction
2. balance oxidation
or oxidation potential. Fluorine, being the most nonmetallic
reduction reactions using
element, has the greatest tendency to undergo reduction or
change in oxidation number.
to gain electrons during a redox process. On the other hand,
metallic elements possess great tendency or potential to lose
electrons or undergo oxidation.

Oxidation and/or Reduction Reactions

A redox process involves the coupled reactions of oxidation and reduction. Oxidation
involves the loss of electrons by the substance being oxidized. The substance that oxidizes is called
the oxidizing agent and causes itself to be reduced during the process. Reduction involves the gain
of electrons by the reduced substance. The substance that reduces it is called the reducing agent
and in turn causes itself to be oxidized.
Balancing Redox Reactions
Redox reactions can be balanced in two ways: by the change in oxidation state method or
by the ion-electron method.
The following steps are involved in balancing redox reactions by the change in oxidation
state method:
3. Determine the element/s which showe an increase or decrease in oxidation state. The oxidizing
agent shows a decrease in oxidation state while the reducing agent shows an increase in oxidation
state. One unit decrease in oxidation state means a gain of one electron while one unit increase in
oxidation state means the loss of one electron. .
4. Determine the number of electrons gained or lost per molecule or unit from the change in
oxidation state.
5. Balance the number of electrons gained and electrons lost
6. Balance the number of atoms of the element oxidized or reduced.
7. Balance the rest of the equation by inspection, balancing H and O last if they are not the element
oxidized or reduced.
 Galvanic Celis

Electrochemistry is the branch of chemistry that

deals with the conversion of electrical energy. It Section Objectives:
involves transfer of electrons from a reducing species to At the end of this section, you
an oxidizing species through a redox reaction. This should be able to:
transfer of electrons during redox reactions is the
guiding principle in the operation of electrochemical 1. Draw the structure of a
cells. galvanic cell and label its
parts;
Half-reaction: A hypothetical reaction that 2. Identify the reaction
shows only the oxidation or reduction. This is used to occurring in the different
partially balance the oxidation or reduction reaction parts of the cell;
only. 3. Write the half-equations
for the reactions occurring
A redox reaction normally occurs when the oxidizing at the electrodes;
agent is in contact with the reducing agent like when the 4. Write the balanced overall
reaction occurs in solution. When zinc metal is added to cell reaction; and
a solution containing copper (II) ions, insoluble copper 5. Give different examples of
metal forms, while on the other hand, soled zinc galvanic cells
dissolves described by the following reaction.

The sum of the electronically balanced half-reactions, reactions (2’) and (3’), gives reaction
(1). The electrons generated in the oxidation reaction are transferred directly from the reducing
agent, Zn(s) to the oxidizing agent, Cu2+ since the two reaction systems are found in the same
solution.
However, if the two reactions are separated physically, like placing the solutions in separate
beakers, a solid conducting wire has to be provided to connect the solutions. The terminals are
directly involved in the redox process and must therefore consist of Zn metal for the Zn2+ solution
and Cu metal for the Cu2+ solution. The terminals are the electrodes -the cathode and the anode.
Reduction occurs at the cathode, while oxidation reaction occurs at the anode. This is shown in
Figure 13.1. The salt bridge (inverted U-tube) contains a strong electrolyte, usually KNO3, which
conducts electricity and allows charges to move across the two solutions without allowing the
solutions to mix. This hinders the buildup of excess positive and negative charges in either
solution.

When spontaneous redox reaction takes place in a setup like the one shown in Figure 13.1,
where the transfer of electrons takes place through an external circuit instead of directly between
the reactants (when all the reacting species are in one container) and the energy released by the
redox reaction is used to perform work, the setup is called a galvanic cell.
In all electrochemical cells:
1. Oxidation occurs at the anode and anions migrate toward the anode within the cell. In the
example in Figure 13.1, SO42- ions move from the cathode toward the anode.
2. Reduction occurs at the cathode and cations migrate toward the cathode within the cell. In
the given example Zn2+ ions are the cations that move toward the cathode.
3. The flow of electrons in the external circuit (where the electrons do the electrical work) is
from the anode to the cathode. The electrons lost during the oxidation at the anode leave
the system through the metal electrode, flow through the wire in the external circuit then
enter the system at the cathode where electrons are used (gained) during the reduction
reaction.
The chemical energy generated by the reaction is given off in the form of electrical energy as
indicated by the positive voltage observed (measured by the attached voltmeter) for the
spontaneous reaction. When the reaction is nonspontaneous such as when polarity of the electrodes
is reversed, a negative voltage is observed.
As the chemical process continues, the electrodes that are actively involved in the redox
process will either be depleted or become coated with atomic layers of the deposited species. In
the example, the Zn(s) electrode will be depleted as it goes into solution in the form of Zn 2+ ions,
while the Cu(s) electrode will be coated with atomic Cu layers, resulting from the reduction of Cu 2+
ions as the reaction proceeds.
 Standard Reduction Potentials

The cell voltage or cell potential is the potential

Section Objectives
At the end of this section,
you shoulid be able to
1. define reduction
potential, Oxidation
potential, and cell potential
2. describe the standard
hydrogen electrode, and
3 calculate the standard cell
potential.
difference between the electrodes of a galvanic cell when no
current flows. It is observed as the voltage reading in the
voltmeter that is connected in series to the galvanic cell at zero
current (no current flows). When the cell potential is positive,
electrical energy is generated during the process and the cell is
galvanic (or voltaic). Galvanic cells result from the conversion
of chemical energy into electrical energy during a spontaneous
reaction. When the cell potential is negative, the cell is not
galvanic but electrolytic, the reaction is nonspontaneous and
requires electrical energy to carry out the redox process.

Standard reduction half-cell potentials, Ɛ°(V), are available from tables of reduction
potentials. By convention, the standard electrode potential always refers to the potential of the
reduction half-reaction. The standard reduction potential values represent the relative tendency of
the species to undergo reduction compared with hydrogen when all the components are in their
standard state. The values are determined against a standard hydrogen electrode (SHE), a standard
reference half-cell that consists of a specially prepared Pt electrode immersed in a 1 M aqueous
solution of a strong acid (to give [H3O+] of 1 M) through which H2(g) at 1.0 atm is bubbled. Thus,
the reference half-reaction for all electrodes is

A positive reduction potential means that the reduction has greater tendency to occur
compared with that of H+ to H2. The standard reduction potential of hydrogen is arbitrarily assigned
a zero (0.00 V) potential value.
 The standard state is the state at which the concentrations of all 1onic species is 1.0 M and
the partial pressure of all gaseous species is 1.0 atm at a standard temperature of 25C
The oxidation potential therefore is a measure of the tendency of a species to undergo
Oxidation. In tables of electrode potentials, values are given only as reduction potentials There are
no tables for oxidation potentials.
Therefore, to determine the oxidation potential for an oxidation half-reaction, simply
change the sign of the reduction potential just like how it is done with AH or AG for a reverse
reaction. However, only the sign of the electrode potential can be changed. Its value remains the
same even when the number of moles of species in the balanced reaction is increased or decreased
by a factor. Note that the Oxidation potential for the half-reaction:
which is the negative value of the reduction potential found in the
table.
The cell potential is the measure of the energy available from a galvanic cell as a result of
the redox reaction that occurs within the cell. It is also called the electromotive force of the cell or
its voltage. A larger cell potential means a larger amount of energy that a given number of electrons
can generate as they travel between the electrodes. A high potential means that the cell reaction
has a strong tendency to produce a current of electrons that will generate a large amount of energy.
The standard cell potential is the cell potential measured when the concentration of each
ion in the reaction is 1M and the pressure of all gases in the reaction is 1 atm. It is obtained from
the sum of the standard reduction potential of the cathode and the standard Oxidation potential of
the anode.

But since only standard reduction potentials are available in tables, and oxidation (not
reduction) occurs at the anode, we can also write

which automatically reverses the sign of the reduction potential of the anode reaction to give the
oxidation potential. The cell potential is determined from the redox reaction obtained from the sum
of the oxidation reaction at the anode and the reduction reaction at the cathode. The cell is galvanic
if the potential is positive, which means that the reaction corresponds to that of a cell that has the
tendency to produce electrical energy. If the cen potential obtained is negative, the electrochemical
cell is electrolytic.
Why should a reference electrode be used in evaluating standard electrode reduction
potentials of various species?
 Spontaneity of Redox Reactions

Section Objectives
In Section 3 of this chapter, it was established that for a
At the end of this section, galvanic cell, the cell reaction is obtained either by adding the
you should be able to anode oxidation half-reaction to the cathode reduction half
reaction or by subtracting the anode reduction half-reaction
1. relate the value of the cell from the cathode reduction half-reaction. The standard cell
potential to the feasibility potential is the sum of the reduction potential of the cathode
of using the cell to generate and the oxidation potential of the anode or the difference
an electric current, and obtained between the cathode reduction potential and the
2. determine the potential anode reduction potential, which gives:
and predict the cell reaction
of some assembled
electrochemical cells.
Therefore, for the reaction of the Zn-Cu cell given in Section 3,
which is the quantity of electrical energy generated by the galvanic cell at the standard state. This
was evaluated from the standard half-cell potential of each half-reaction. Since the cell potential
is positive, the cell is classified as galvanic at the standard state. Whether a cell is galvanic or
electrolytic can be determined just by comparing the values of the electrode potentials. If the
cathode potential is more positive (greater reduction potential), than the anode reduction potential,
then the cell potential is positive and the cell is galvanic.
Note that the standard cell potential was determined without a balanced chemical equation. This
can be done only because the balanced chemical reaction is not necessary if one needs to evaluate
only the standard cell potential. Remember that potentials are intensive properties, hence, the
values are not dependent on the Coefficient in the balanced equation.
The amount of reaction free energy, ΔG, the energy released or used by a reaction, is
proportional to the cell potential. As the cell potential increases, the higher is the amount of
reaction free energy that can be obtained from the cell. A positive cell potential means that reaction
free energy is released thus ΔG is negative, which corresponds to a spontaneous process (Chapter
9, Section 3). This means that for galvanic cells, the more positive the cell potentials, the greater
is the amount of energy produced. On the other hand, a negative cell potential means that the
reaction needs the application of energy to occur, ΔG is positive and the reaction is
nonspontaneous. The reaction free energy, ΔG, and the cell potential, E, are related by the
equation:
Cell representative
By convention, a cell is generally represented as follows:
Anode | Oxidation Process | | Reduction process | Cathode
Since the standard cell potential is evaluated by subtracting the standard half-cell
potential of the anode from the cathode:

It follows that from the cell representation:

Sample Problem:
Write the cell representation of the cell where the reaction:

takes place and determine its standard cell potential. If the cell is electrolytic, make it galvanic
and write the corresponding cell representation.

Solution:
Since the Cu electrode is oxidized and the Zn electrode is reduced, Cu is the anode and
Zn is the cathode. The cell representation will therefore be:
Substituting,

The electrolytic cell can be converted into a galvanic cell by changing the polarity of the
electrodes thereby interchanging the cathode and the anode reactions to come up with:
 Commercial Cells and Batteries

Commercial cells use the electrochemistry to generate

Section Objective
the current that we derive from them. They derive chemical
At the end of this
energy from the reactions that occur in the cells and in turn
section you should be able to
convert the chemical energy to electrical energy. describe the electrochemistry
This module describes some cells that are commonly involved in some common
batteries ( Leclanche dry cell,
used. Which of these cells have you used?
button batteries, fuel cells lead
storage battery )
The Leclanche Dry Cell
This is the most common cell used in flashlights, radios, some calculators, and the like. It is
one of the first modern electrical batteries that was invented by the French electrical engineer,
Georges Leclanche. The zinc casing acts as the anode and a graphite rod is the cathode. The
following reactions are responsible for the electrical energy derived from this cell.

Mercury and Silver Button Battery

Mercury is used to inhibit corrosion that can lead to gas buildup which in turn can cause
bulging and leakage or can adversely affect battery performance.
 Chemistries of miniature battery differ in design, voltage, capacity, shelf life, and other
characteristics. Zinc air batteries are mostly used in hearing aids and ear implants, and also found in
pagers. Silver oxide batteries are most frequently used in watches, clocks calculators, games and
cameras. Alkaline batteries, a variant of the Leclanche dry cell, which are dependent on the reaction
between Zn(s) and MnO2(s) with KOH(aq) as the electrolyte, are often used in applications such as toys,
key chains, and remote controls. The following reactions occur at the electrodes.

Fuel Cells
The cells convert the energy of a fuel to electrical energy and are used for portable power
generation, stationary power generation, and power for transportation.
The following reactions occur in a hydrogen-oxygen fuel cell.
Lead Storage Batter
This is the battery used in cars and trucks. A typical 12-V battery consists of 6 cells
connected in series to give a total potential of 12 Vin the form of several Pb plates dipped in H 2SO4
solution. When the battery discharges, it generates electrical energy as a galvanic cell. When it
recharges it uses electrical energy as an electrolytic cell where the half-cell reactions and the overall
reaction is reversed.
 Corrosion

The term corrosion refers to the process of deterioration of

Section Objective
metals. Although this process is usually describes in terms of the
At the end of this module, metal iron, it is not limited to iron but can happen to any metal that
you should be able to apply has lower reduction potential than that of hydrogen.
electrochemical properties
If the function of cells is a positive application of
to explain corrosion.
electrochemistry, corrosion is the application of electrochemistry
with negative effect. The electrochemical nature of corrosion can be
deducted from the nature of the four major components necessary for corrosion to occur, namely;
• A metal anode where corrosion will take place;
• A cathode where no corrosion will take place;
• An electrolyte which can be soil, water, moisture, etc; and
• An electrolyte connection between the metal anode and the cathode

Corrosion of steel occurs when the major component of steel, iron (Fe) at the surface of a steel
component undergoes a number of simple changes. If we consider the corrosion reaction as an
electrochemical reaction, then the electrode reactions will be:

Note that the reaction potential is positive which means that the reaction is spontaneous. The
reaction also shows that the oxidation of iron is favored by acidic conditions indicated by the presence
of hydrogen ions at the cathode.
The Fe2+(aq) produced at the anode is oxidized by the O2(g) in air to Fe3+ which forms iron (III)
oxide in the hydrated form. This hydrated iron (III) oxide is what we call rust.

To prevent corrosion of iron, the metal can be coated with a substance that cannot be oxidized
like a coat of paint or with a metal that is easier to oxidize than iron. This is the basis of galvanization
of iron where the iron is coated with zinc metal to protect the iron from corrosion. The reduction
potentials (see Table 13.1) of Fe 2+ and Zn2+ show that Fe2+ is more easily reduced than Zn 2+ which
means that Zn is more easily oxidized than Fe and will therefore act as the anode; Fe, in turn, will act
as the cathode at which O2(g) is reduced.

Reference:
General Chemistry 2 (First Edition)
Authors:
Luciana V. Ilao
Betty M. Lontoc
Edwehna Ellinore S. Paderna-Gayon
Coordinator:
Josefina Gironella-Belen