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Discussion
Electrochemistry
Electrochemistry is the study of the interconversion of electrical and chemical energy. This
conversion takes place in an electrochemical cell that may be a (n)

 Voltaic (galvanic) cell, in which a spontaneous reaction generates electrical energy.

 Electrolytic cell, in which electrical energy is used to bring about a nonspontaneous
reaction.

All of the reactions considered in this chapter are of the oxidation-reduction type. A reaction can
be split into two half-reactions. In one half-reaction, referred to as reduction, electrons are
consumed; in the other, called oxidation, electrons are produced. There can be no net change
in the number of electrons; the number of electrons consumed in reduction must be exactly
equal to the number produced in the oxidation half-reaction. These two half-reactions combine
to give a balanced redox reaction.

In an electrochemical cell, these two half-reactions occur at two different electrodes,

which most often consists of metal plates or wires. Reduction occurs at the cathode; a typical
half-reaction might be

reduction
cathode: Cu2+(aq) + 2e – Cu (s)

Oxidation takes place at the anode, where a species such as zinc metal produces electrons:
oxidation
anode: Zn (s) Zn2+(aq) + 2e –

It is always true that in an electrochemical cell, anions move to the anode; cations move to the
cathode.
One of the most important characteristics of a cell is its voltage, which is a measure of
reaction spontaneity. Cell voltages depend on the nature of the half-reactions occurring at the
electrodes and on the concentrations of species involved. From the voltage measured at
standard concentrations, it is possible to calculate the standard free energy change and the
equilibrium constant of the reaction involved.
The principles discussed in this chapter have a host of practical applications. Whenever
you start your car, turn on your cell phone, or use a remote control for your television or other

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devices, you are making use of a voltaic cell. Many of the most important elements, including
hydrogen and chlorine, are prepared in electrolytic cells.

Oxidation-Reduction Reactions
Review of Oxidation-Reduction Terminology and Concepts
 A redox reaction involves a transfer of electrons between two species.
 Oxidation occurs when a species loses electrons and increases its oxidation number (O.N.).
An equation that shows this loss is called an oxidation half-reaction. In this half-reaction, the
electrons are in the product side.
 Reduction occurs when a species gains electrons and decreases its oxidation number
(O.N.). An equation that shows this gain is called a reduction half-reaction. In this half-
reaction, the electrons are in the reactant side.
 The ion or molecule that donates the electrons (i.e., oxidized) is called the reducing agent.
 The ion or molecule that accepts the electrons (i.e., reduced) is called the oxidizing agent.
 Oxidation and reduction occur together in the same reaction. There is no net change in the
number of electrons, just an exchange of electrons.

Balancing Half-Equations (Oxidation or Reduction)

Before you can balance an overall redox equation, you have to be able to balance two half-
equations, one fore oxidation (electron loss) and one for reduction (electron gain). Sometimes
that’s easy. Given the oxidation half-reaction

Fe2+(aq) Fe3+(aq) (O.N. Fe: +2 +3)

it is clear that mass and charge balance can be achieved by adding an electron to the right:
Fe2+(aq) Fe3+(aq) + e–

In another case, this time a reduction half-equation,

Cl2(g) Cl– (aq) (O.N. Cl: 0 –1)
mass balance is obtained by writing a coefficient of 2 for Cl–; charge is the balanced by adding
two electrons to the left. The balanced half-equation is

Cl2(g) + 2 e– 2 Cl– (aq)

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Sometimes, though, it is by no means obvious how a given half-equation is to be

balanced. This commonly happens when elements other than those being oxidized or reduced
take part in the reaction. Most often, these elements are oxygen (O.N. = – 2) and hydrogen
(O.N. = +1). Consider, for example, the half-equation for the reduction of the permanganate ion,

MnO4– (aq) Mn2+(aq) (O.N. Mn: +7 +2)

or the oxidation of chromium(III) hydroxide,
Cr(OH)3 (s) CrO42– (aq) (O.N. Cr: +3 +6)

To balance half-equations such as these, proceed as follows:

a) Assign oxidation numbers to each element.

b) Balance the atoms of each element being oxidized or reduced.
c) Multiply the oxidation number by the number of atoms that have that oxidation
number. This gives you the “total” oxidation number.
The number of atoms is indicated either by the coefficient that you used to balance the
atoms or by the subscript of the atom.
d) Balance oxidation number by adding electrons.
Electrons are added to the left for a reduction half-equation and to the right for an
oxidation half-equation
The number of electrons added should equal the change in “total” number from part (c).
e) Balance charge by adding H+ ions in acidic solution and OH –
ions in basic
solution.
f) Balance hydrogen by adding H2O molecules.
g) Check to make sure that oxygen is balanced.
If it is, the half-equation is almost certainly balanced correctly with respect to mass and
charge.

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EXAMPLE 1:
1. BrO– Br2
assign oxidation numbers (O.N.)
Br = +1 Br = 0
atom balance
1 Br 2 Br
x2
(2) BrO– Br2
total O.N. (atoms x O.N.)
2(+1) = 2 2(0) = 0
O.N. decrease by 2
reduction: 2e– on reactant side
2 e– + 2 BrO– Br2
medium?

2. In solution 3. In solution
ACID BASE

2 e– + 2 BrO– Br2 2 e– + 2 BrO– Br2

Charge Balance Change balance

2(–1) + 2(–1) 2(0) 2(–1) + 2(–1) 2(0)

–4 0 –4 0
Balance with H+ Balance with OH–

4H+ + 2e– + 2 BrO– Br2 2e– + 2 BrO– Br2 + 4OH–

H balance H balance

4H atoms OH atoms OH atoms 4H atoms

Balance with H2O Balance with H2O

4H+ + 2e– + 2 BrO– Br2 + 2H2O 2H2O + 2e– + 2 BrO– Br2 + 4OH–

Balancing Redox Equations

The process used to balance an overall redox equation is relatively straightforward, provided
you know how to balance half-equations. Follow a systematic, four-step procedure:

1) Split the equation into two half-equations, one fore reduction, the other for oxidation.
2) Balance one of the half-equations with respect to both atoms and charge as described
above (steps a through e).
3) Balance the other half-equation.
4) Combine the two half-equations in such a way as to eliminate electrons.

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EXAMPLE 2:
Balance the following redox reactions by following the four step process outline above.
a) Fe2 (aq) + NO3– (aq) Fe3+ (aq) + NO (g) (basic solution)

SOLUTION

1. Split into two half- Fe2+ (aq) Fe3+ (aq)

equations.
NO3– (aq) NO (g)
2-3. Balance the half- Check the text. This has been done earlier.
equations.
Fe2+ (aq) Fe3+ (aq) + e–
NO3– (aq) + 3 e– + 2H2O NO (g) + 4OH– (aq)
4. Eliminate electrons Multiply the oxidation half-equation by 3.
3 [Fe2+ (aq) Fe3+ (aq) + e–]
Combine half-equations. NO3 (aq) + 3 Fe2+ (aq) + 2H2O
–
NO(g) + 4OH– (aq) +3Fe3+ (aq)

b) MnO4– (aq) + Cl2 (g) Mn2+ (aq) + ClO3– (aq) (acidic solution)

SOLUTION

1. Split into two half- MnO4– (aq) Mn2+ (aq)

equations.
Cl2 (g) ClO3– (aq)
2-3. Balance the half- The oxidation half-equation is balanced in Example 1.
equations.
Cl2 (g) + 6 H2O 2 ClO3– (aq) + 10 e– + 12 H+ (aq)
Try to balance the reduction half-equation.
4. Eliminate electrons Multiply the reduction half equation by 2.
2[MnO4– (aq) + 8 H+ (aq) + 5 e– Mn2+ (aq) + 4 H2O
Combine half-equations. Cl2 (g) + 6 H2O + 2 MnO4– (aq) + 16 H+ (aq) 2 ClO3– (aq) + 12 H+ (aq) +
2 Mn2+ (aq) + 8 H2O
Net ionic equation 6 H2O 8 H2O = 2 H2O (product side)
16 H+ 12 H+ = 4 H+ (reactant side)
Balanced net ionic Cl2 (g) + 2 MnO4– (aq) + 4 H+ (aq) 2 ClO3– (aq) + 2 Mn2+ (aq) + 2 H2O
equation

? SAQ 1

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1. Give the oxidation half – reaction and the reduction half – reaction of the equation
below:
Cu + 2 AgNO3 2 Ag + Cu (NO3)2

SAQ 2
1. Balance the following half – equations.
a. NO3- NH4+ in acidic medium
3+
b. Fe Fe in basic medium

SAQ 3
1. Write the balance equations for the reactions below:
a. P4 + Cl- PH3 + Cl2 in acid solution
b. Ca + VO43- Ca2+ + V2+ in basic solution

Voltaic Cells
In principle at least, any spontaneous redox reaction can serve as a source of energy in a
voltaic (galvanic cell). The cell must be designed in such a way that oxidation occurs at one
electrode (anode) with reduction at the other electrode (cathode). The electrons produced at the
anode must be transferred to the cathode, where they are consumed. To do this, this electrons
move through an external circuit, where they do electrical work.

To understand how a voltaic cell operates, let us start with some simple cells that are
readily made in the general chemistry laboratory.

The Zn-Cu2+ Cell

When a piece of zinc is added to a water solution containing Cu 2+ ions, the following redox
reaction takes place:

Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s)

In this reaction, copper metal plates out on the surface of the zinc. The blue color of the
aqueous Cu2+ ion fades as it is replaced by the colorless aqueous Zn2+ ion (Figure 1). Clearly,
this redox reaction is spontaneous; it involves electron transfer from a Zn atom to a Cu2+ion.

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Figure 1. Zn-Cu2+ spontaneous redox reaction. The blue of the Cu2+ ion in solution fades (from left to
right) as the ion is reduced to metallic Cu that deposits on the zinc strip in the solution.

Figure 2. A Zn-Cu2+ voltaic cell. In this voltaic cell, a voltmeter (left) is connected to a half-cell consisting of a Cu
cathode in a solution of blue Cu2+ ions and a half-cell consisting of a Zn anode in a solution of colorless Zn 2+ ions. The
following spontaneous reaction takes place in this cell: Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s). the salt
bridge allows ions to pass from one solution to the other to complete the circuit and prevents direct contact between
Zn atoms and the Cu2+ ions.

To design a voltaic cell using the Zn-Cu 2+ reaction as a source of electrical energy, the
electron transfer must occur indirectly; that is, the electrons given off by zinc atoms must be
made to pass through an external electric circuit before they reduce Cu 2+ ions to copper atoms.
(Figure 2) shows one way to do this. The voltaic cell consists of an anode half-cell and a
cathode half-cell:

 a Zn anode dipping into a solution containing Zn 2+ ions, seen in the breaker at the far
right.
 a Cu cathode dipping into a solution containing Cu 2+ ions (blue), seen in the other
breaker in (Figure 2).

The “external circuit” consists of a voltmeter with leads (red and black) to the anode and
cathode.

Let us trace the flow of electric current through the cell.

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1) At the zinc anode (connected to the black wire in Figure 2), electrons are produced by
the oxidation half-reaction

Zn (s) Zn2+ (aq) + 2 e–

This electrode, which “pumps” electrons into the external circuit, is ordinarily marked as
the negative pole of the cell.

2) Electrons generated at the anode more through the external circuit (right to left in Figure
2) to the copper cathode, connected through the red wire to the voltmeter. At the
cathode, the electrons are consumed, reducing Cu 2+ ions present in the solution around
the electrode:
Cu2+ (aq) + 2 e– Cu (s)

The copper electrode, which “pulls” electrons from the external circuit, is considered to
be the positive pole of the cell.

3) As the above half-reactions proceed, a surplus of positive ions (Zn 2+) tends to build up
around the zinc electrode. The region around the copper electrode tends to become
deficient in positive ions as Cu2+ ions are consumed. To maintain electrical neutrality,
cations must move toward the copper cathode or, alternatively, anions must move
toward the zinc anode. In practice, both migrations occur.

In the cell in Figure 2, movement of ions occurs through a salt bridge connecting the two
beakers. The salt bridge is an inverted glass U-tube, plugged with glass wool at each end.
The tube is filled with a solution of a salt that takes no part in the electrode reactions;
potassium nitrate, KNO3, is frequently used. As current is drawn from the cell, K + ions move
from the salt bridge into the cathode half-cell. At the same time, NO 3– ions move into the
anode half-cell. In this way, electrical neutrality is maintained without Cu 2+ ions coming in
contact with the Zn electrode, which would short-circuit the cell.

The cell in Figure 2 is often abbreviated as Zn | Zn2+ || Cu2+ | Cu

In this notation,

 The anode reaction (oxidation) is shown at the left. Zn atoms are oxidized to Zn2+ ions.
 The salt bridge (or other means of separating the half cells) is indicated by the symbol ||.

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 The cathode reaction (reduction) is shown at the right, Cu2+ ions are reduced to Cu
atoms.
 A single vertical line indicates a phase boundary, such as that between a solid electrode
and an aqueous solution.

Notice that the anode half-reaction comes first in the cell notation, just as the letter a comes
before c.

Cell Notation
A description of a half-cell must contain the following:

- The nature of the electrode materials.

- The nature of the electrolytes in contact with the electrodes (with the concentration of
ions in solution).
- The reactants and products in the half-reactions.

In writing half-cell notations, the oxidized species is written first followed (going to the right) by
the reduced species then the electrode material. Sometimes the latter two are the same. The
following are used to separate the species from each other:

comma (,) between species which are in the same phase like two ions in solution

and single vertical bar ( | ) between species in different phases.

Thus the two half-cells in the electrochemical cell described earlier are represented as
follows:

Zn2+ (aq) | Zn(s) Cu2+ (aq) | Cu(s)

The following half-cell reactions do not involve a solid conductor.
Fe3+ (aq) + e–  Fe2+ (aq)
Br2 (aq) + 2e–  2 Br– (aq)
In these cases, the half-cell is constructed by using an inert electrode like platinum or graphite.
Thus the half-cells are represented as follows:

Fe3+ (aq), Fe2+ (aq) | C(graphite)

Br2 (aq), Br– (aq) | Pt

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The cell represented as

H3O+ (aq) | H2 | Pt
Is the hydrogen half-cell consisting on an acidic solution containing H3O+ into which hydrogen
gas, H2, is bubbled at a platinum electrode.
To represent a complete cell, we simply put the symbols of the two half-cells with the f
ollowing conversations:

- The anode half-cell is written on the left and the cathode half-cell on the right.
- The anode half-cell notation in reversed; this results in the electrode materials being
written on the two ends of the notation.
- The salt bridge is denoted by double vertical bar (II); this separates the anode from the
cathodic compartments.
Thus, the electrochemical cell earlier described is represented by:
Zn (s) | Zn2+ (aq) || Cu2+ (aq) | Cu (s)
Example 1
Write the electrode reactions for the cell represented as:
Mg | Mg2+ || Ag+ | Ag.
Answer:
In the cell notation the anode is written first followed by the cathode, thus
Oxidation half-reaction: Mg  Mg2+ + 2 e–
Reduction half-reaction: Ag+ + e–  Ag
Mg is oxidized at the anode ang Ag+ is reduced at the cathode.
Example 2
For the cell represented as A1 | A13+ || Pb2+ | Pb
a. Identify the anode and the cathode.
b. Write the half-cell reactions.
c. Write the balanced equation for the overall reaction.
Answer:
a) In writing cell notations, the anode and anodic components are written on the
left and the cathode and cathodic components on the right. Thus the anode
material is A1 and the cathode is Pb.
b) Thus, the anode reaction or oxidation is:

Oxidation: Al (s)  Al 3+ + 3e–

And the cathode reaction or reduction reaction is:

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Reduction: Pb2+ + 2e–  Pb (s)

c) To obtain the overall reaction, first balance the half-reactions by writing
appropriate coefficients to balance the number of electrons lost and gained.

Oxidation: 2 [Al (s)  Al3+ + 3e–]

Reduction: 3 [Pb2+ 2e–  Pb (s)]
2 Al (s) + 3 Pb2+  2 Al3+ 3 Pb (s)

? SAQ 4
1. Write the cell notation for the galvanic cell with the cell reaction:
2 Al + 3 Sn2+ 2 Al3+ + 3 Sn

Standard Voltages
The driving force behind the spontaneous reaction in a voltaic cell is measured by the cell
voltage, which is an intensive property, independent of the number of electrons passing through
the cell. Cell Voltage depends on the nature of the redox reaction and the concentrations of the
species involved; for the moment, we’ll concentrate on the first of these factors.

The standard cell voltage (Eº) (also referred to as the standard voltage) for a given cell
is that measured when the current flow is essentially zero, all ions and molecules in solution
are at a concentration of 1 M, and all gases are at a pressure of 1 atm. To Illustrate,
consider the Zn-H+ cell. Let us suppose that the half-cells are set up in such a way that the
concentrations of Zn2+ and H+ are both 1M and the pressure of H 2 (g) is 1 atm. Under these
conditions, the cell voltage at very low current flow is +0.762 V. This quantity is referred to as
the standard voltage and is given the symbol Eº.

Zn (s) + 2 H+ (aq, 1 M)  Zn2+ (aq, 1 M) + H2 (g, 1atm) Eº = +0.762 V

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E⁰red and E⁰ox

Any redox reaction can be split into two half-reactions, an oxidation and a reduction. It is
possible to associate the standard voltages, standard oxidation voltage (Eºox) and standard
reduction voltage (Eºred), with the oxidation and reduction half-reactions. The standard voltage
for the overall, Eº, is the sum of these two quantities.

Eº = Eºred + Eºox
Example
Consider the voltaic cell in which the reaction is
2Ag+ (aq) + Cd (s)  2Ag (s) + Cd2+ (aq)
a. Use the table to calculate Eº for the voltaic cell.

Strategy
1. Assign oxidation numbers to each element so you can decide which element is reduced
and which one in oxidized.
2. Write the oxidation and reduction half-reactions together with the corresponding Eºox and
Eºred.
3. Add both half-reactions (make sure you cancel electrons) and take the sum of Eºox and
Eºred to obtain Eº for the cell.

Solution
1. Oxidation numbers Ag: +1  0 (reduction)
Cd: 0  +2 (oxidation)
2. Half-reactions 2 Ag+ (aq) + 2 e–  2 Ag (s) Eºred = +0.799 V
Cd (s)  Cd2+ (aq) + 2e– Eºox = - (Eo red) = - (-0.402 V)
= +0.402 V
3. Eº Cd (s) + 2 Ag+ (aq)  Cd2+ (aq) + 2Ag (s) Eº = 0.799 V + 0.402 V
= 1.201 V

? SAQ 5
1. Compute the voltage (use Table 1. STANDARD REDUCTION POTENTIAL) that would
result if half-cells were combined. State which reaction is oxidation and which is
reduction. Identify the anode and the cathode.
Au Au3+ + 3 e –
Ag Ag+ + 1 e –

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Summary
Electrochemistry is the study of the interconversion of electrical and chemical energy.

Voltaic (galvanic) cell, in which a spontaneous reaction generates electrical energy.

Electrolytic cell, in which electrical energy is used to bring about a nonspontaneous reaction.

A redox reaction involves a transfer of electrons between two species.

Oxidation occurs when a species loses electrons and increases its oxidation number (O.N.). An

equation that shows this loss is called an oxidation half-reaction. In this half-reaction, the

electrons are in the product side.

Reduction occurs when a species gains electrons and decreases its oxidation number (O.N.).

An equation that shows this gain is called a reduction half-reaction. In this half-reaction, the

electrons are in the reactant side.

The ion or molecule that donates the electrons (i.e., oxidized) is called the reducing agent.

The ion or molecule that accepts the electrons (i.e., reduced) is called the oxidizing agent.

Cell Voltage depends on the nature of the redox reaction and the concentrations of the species

involved; for the moment, we’ll concentrate on the first of these factors.

The standard cell voltage (Eº) (also referred to as the standard voltage) for a given cell is that

measured when the current flow is essentially zero, all ions and molecules in solution are at

a concentration of 1 M, and all gases are at a pressure of 1 atm.

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References
Brown, Le May and Bursten, Burdge, 2004, Chemistry The Central Science (9 th edition),
Pearson Education (Asia) Pte Ltd.

Cengage Learning Asia Ltd., 2019, General Chemistry 2 (Philippine edition),

Rex Book Store Inc.

Malone, Leo J., Dolter, Theodore D., 2010, Basic Concepts of Chemistry (8 th edition),
John Wiley and Sons, Inc.

Masterton, William L., Hurley, Cecile H., Peterson, James F., Sack, Dorothy. Gabler,
Robert E., 2018, Chemistry for Engineering Students (Philippine edition),
C & E Publishing, Inc.

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Answer of Self-Assessment Questions (ASAQ)

SAQ 1
1. Oxidation : Cu0 Cu2+ + 2e –
Reduction: 2 Ag + 2e –
+
2 Ag0

SAQ 2
1. a. NO3– + 8 e – + 10 H+ NH4+ + 3 H2O
b. Fe+ + 3 e – Fe

SAQ 3
1. a. P4 + 12 Cl – + 12 H+ 4 PH3 + 6 Cl2
b. 3 Ca + 8 H2O + 2 VO43 – 3 Ca2+ + 2 V2+ + 16 OH–

SAQ 4
1. Al | Al3+ || Sn2+ | Sn

SAQ 5
1. Oxidation: anode Ag Ag+ + 1 e –
Reduction: cathode Au + 3 e –
3+
Au

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