ELCTROCHEMISTRY

Overview
This topic details the chemistry behind electricity. Concepts and principles involved are supported with
real-life applications such as batteries, fuel cell, electric energy consumption and cost among others.

Outcome
At the end the topic, the student should be able to:

 Understand redox reaction

 Calculate cell potentials using standard reduction potentials under standard and non-standard
condition
 Predict whether the redox reaction is spontaneous or non-spontaneous
 Solve problems in electrolysis
 Identify different types of batteries
 Understand the chemistry behind electricity in daily life

Introduction
Distinct metals corrode differently. For an instance, aluminum has a greater tendency to corrode than iron,
but corrosion of aluminum is not problematic compared to iron. The aluminum oxide corrosion product
forms a protective layer on the surface of aluminum metal while the iron oxide corrosion product flakes
off the surface of iron, exposing fresh iron to corrosion.

Figure 1: Corrosion occurs in a variety of forms. The chain shows

uniform corrosion (left). The grill cover shows crevice corrosion where
the handle is attached (right).
Electrode Potential

Reactions that transfer electrons between reactants are known as oxidation-reduction or redox reactions.
Oxidation is a process where electrons are by a substance and reduction is a process where electrons are
gained by a substance.

For an oxidation-reduction reaction to occur one reactant must be oxidized and one reactant must be
reduced. Oxidation cannot occur without reduction. For example, when copper wire is placed in a silver
nitrate solution, a redox reaction occurs. A reaction is observed to occur because the solution changes
color and crystals form on the surface of the copper wire, see Figure 2.

Figure 2: When a clean copper wire is placed into a colorless solution of silver nitrate, it is quickly
apparent that a chemical reaction occurs: silver metal forms on the copper wire and the solution turns
blue.

The solution’s blue color is indicative of Cu2+ ions in solution. Cu2+ is formed when a copper atom loses
two electrons. The copper metal (Cu) is oxidized.
2+
𝐶𝑢(𝑠) → 𝐶𝑢(𝑎𝑞) + 2𝑒 −

The crystals forming on the surface of the copper wire are silver metal (Ag). Silver is formed when a
silver cation (Ag+) gains an electron. The silver cation is reduced.
+
𝐴𝑔(𝑎𝑞) + 1𝑒 − → 𝐴𝑔(𝑠)

For the reaction between silver cation and copper metal, two half-reactions are written: one for the
oxidation of copper and one for the reduction of silver. Neither half-reaction can occur without the other.
The half-reactions as written indicate that Ag+ only accepts one electron whereas Cu loses two electrons.
The electron transfer must balance, so the reduction half-reaction is multiplied by 2.

2[𝐴𝑔(+𝑎𝑞) + 𝑒 − → 𝐴𝑔(𝑠) ]
+
= 2𝐴𝑔(𝑎𝑞) + 2𝑒 − → 2𝐴𝑔(𝑠)

Add the two half-reactions together the electrons cancel out leaving the net ionic equation for the redox
reaction.

𝐶𝑢(𝑠) → 𝐶𝑢2+
(𝑎𝑞) + 2𝑒
−

+
2𝐴𝑔(𝑎𝑞) + 2𝑒 − → 2𝐴𝑔(𝑠)
+ 2+
𝐶𝑢(𝑠) + 2𝐴𝑔(𝑎𝑞) → 𝐶𝑢(𝑎𝑞) + 2𝐴𝑔(𝑠)

The substance oxidized is referred to as reducing agent.

• The Cu was oxidized and is the reducing agent.

• The Cu facilitated the reduction of Ag+ by losing electrons.

The substance reduced is referred to as oxidizing agent.

• The Ag+ was reduced and is the oxidizing agent.

• The Ag+ facilitated the oxidation of Cu by gaining electrons.

Galvanic Cell

A galvanic cell is any electrochemical cell in which a spontaneous chemical reaction can be used to
generate an electric current. The name electrochemistry comes from the observation of electric currents in
galvanic cells.

To harness electricity from a galvanic cell, each half-reaction is prepared separately in half-cells. Cu
metal immersed in Cu2+ solution is one half-cell while Ag metal immersed in Ag+ solution is the second
half-cell. Figure 3 shows the galvanic cell set-up.
 Figure 3: Galvanic Cell

A salt bridge is crucial to a galvanic cell. The salt bridge allows ions to flow between each halfcell,
completing the circuit. Current flows by the migration of ions in solution. To transfer current between the
half-cells, a salt bridge is used. The salt bridge contains a strong electrolyte that allows either cations or
anions to migrate into the solution where they are needed to maintain charge neutrality. A metal wire
cannot transport ions and cannot be used. For a salt bridge composed of NH4Cl:

 𝑁𝐻4+ will flow into the 𝐴𝑔+ beaker to offset the removal of 𝐴𝑔+ from solution.
 𝐶𝑙 − will flow into the 𝐶𝑢2+ beaker to offset the production of 𝐶𝑢2+ in solution.

The circuit is completed by connecting wires to each metal strip. A voltage potential of 0.46 V will be
measured for the described cell.

Electrodes are the electrically conducting sites at which either oxidation or reduction occurs.

 The electrode where oxidation occurs is the anode.

 The electrode where reduction occurs is the cathode.

A cell notation is a shorthand notation for the specific chemistry of an electrochemical cell.

 Cell notation lists the metals and ions involved in the reaction.
 A vertical line, |, denotes a phase boundary.
 A double vertical line, ||, denotes a salt bridge.
 The anode is written on the left, the cathode on the right.
General form of cell notation

anode|anode electrolyte||cathode electrolyte|cathode

For the previous example of copper and silver, the electrolyte concentration is also given.
2+ +
(𝑠) |𝐶𝑢(𝑎𝑞) (1 𝑀)|| 𝐴𝑔(𝑎𝑞) (1 𝑀)|𝐴𝑔(𝑠)

An electrochemical cell is at its standard state when the electrolyte concentrations are 1 M. Meanwhile,
for half-cells that generate or consume a gas, a partial pressure of 1 atm is required for the standard state.

Problem 1

Confirm that the potential of the following galvanic cell is 0.462 V:

𝐶𝑢(𝑠) |𝐶𝑢2+ +
(𝑎𝑞) (1 𝑀)|| 𝐴𝑔(𝑎𝑞) (1 𝑀)|𝐴𝑔(𝑠)

Problem 2

Using standard reduction potential, identify the anode and the cathode and determine the cell potential for
a galvanic cell composed of copper and iron. Assume standard conditions.

The Standard Hydrogen Electrode

The standard hydrogen electrode (SHE) is the choice for the standard component in cell potential
measurements. The cell is constructed of a platinum wire or foil as the electrode. The electrode is
immersed in a 1 M HCl solution through which H 2 gas with a pressure of 1 atm is bubbled. The SHE has
been chosen as the reference point for the scale of standard reduction potentials, and assigned a potential
of exactly zero volts. Figure 8 shows the SHE cell.

Figure 8: SHE Cell set-up

Standard Reduction Potentials

To compare the oxidation-reduction trends of species used in electrochemistry, all half-cell potentials are
written as reductions. A table of standard reduction potentials lists the potential of any half-reaction when
connected to a SHE (Table 1). All materials are 1 M for aqueous species and 1 atm partial pressure for
gases.
Table 1: Standard Reduction Potentials for Several Half-Reactions Involved in the Cells

Although the half-reactions are listed as reductions in the table, one half-reaction in any electrochemical
cell must be an oxidation and, therefore, reversed from what appears in the table. The cell potential sign
must be changed when writing the half-reaction as an oxidation. Some half-reactions have positive
potentials, whereas others have negative potentials.
All potentials are measured with a SHE connected to the positive terminal. If the voltage is positive, the
SHE is the anode, the oxidation site. A positive standard reduction potential means the half-reaction
proceeds as written (reduction occurs). If the voltage is negative, the SHE is the cathode, the reduction
site. A negative standard reduction potential means the half-reaction proceeds as an oxidation.
The tendency for the chemicals involved in a half-reaction to be an oxidation or reduction depends on the
value of the reduction potential. A large, positive value for the standard reduction potential implies the
substance is reduced readily and a good oxidizing agent. A large, negative value for the standard
reduction potential implies the substance is oxidized readily and a good reducing agent.
For a galvanic cell, the half-reaction with the more positive reduction potential will be the cathode. The
half-reaction with the more negative reduction potential will be the anode. The standard reduction
potential for any pair of half-reactions, E° cell, is calculated from the standard reduction potentials for the
cathode and anode.

° ° °
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑟𝑒𝑑 − 𝐸𝑜𝑥
 ° °
𝐸𝑟𝑒𝑑 is the standard reduction potential for the cathode and 𝐸𝑜𝑥 is the standard reduction potential for the
anode.

Atomic Perspective on Galvanic Cells

Before half-cells are connected by a salt bridge, a small build up of charge occurs for each half-cell at the
interface between the electrode and the electrolyte. At the anode, some oxidation occurs and cations
dissolve into solution, leaving a negative charge on the anode. At the cathode, some reduction occurs and
cations are removed from solution, leaving a positive charge on the cathode.
Equilibrium can be described for each half-cell, the half-reaction equilibrium. Not oxidationreduction
equilibrium. The build-up of charge on the electrode means there is potential for electrical work. This
potential is the cell potential, or electromotive force (EMF).

Figure 4: Without a salt bridge to close the circuit,

local charges build up around both electrodes.

Galvanic Corrosion and Uniform Corrosion

Metals in contact with a solution establish oxidation half-reaction equilibrium. If the solution contains a
substance that can undergo reduction, a redox reaction may occur. For two metals in contact, such as tin-
plated steel can exposure to air and moisture results in rapid corrosion. The half-reaction equilibrium for
the tin facilitates the process by which iron is oxidized. This is an example of galvanic corrosion.
Figure 5: A “tin can” is usually tin-plated steel. If the tin coating is scratched to expose the underlying
steel, iron in the steel will corrode rapidly.

Metal not in contact with another metal can also corrode. A nonmetal is involved in the second half-cell.
For the corrosion of iron, iron is one half-cell and oxygen dissolved in water is the second half-cell. The
electrode for the oxygen half-cell is the iron itself. Dissolved salts facilitate the corrosion reaction. This is
an example of uniform corrosion.

Figure 6: Iron is oxidized, and oxygen from the air is

reduced. Water is needed for ion mobility between the
anodic and cathodic regions.
Cell Potentials

The relative corrosivities of various plated steels can be expressed as cell potential. A voltmeter measures
the size of the electrical potential and also its polarity - the locations of the negative charge (negative
pole) and the positive charge (positive pole). An electric potential has a fixed polarity and voltage.
Reversing the poles of a battery with respect to a voltmeter changes the sign on the measured voltage but
does not influence the electrochemical reaction in the battery.

Measuring Cell Potential

When a voltmeter is connected to the previously described copper/silver cell, a potential of 0.462 V is
measured. Connecting the copper half-cell to a reducing iron (III)/iron (II) half-cell, a cell potential of
0.434 V is measured. Connecting the iron (III)/iron (II) half-cell to the silver half-cell, results in a cell
potential of 0.028 V. For the three cell potentials measured, the fact that 0.462 V = 0.434 V + 0.028 V
suggests two things:

 The behavior of cell potentials is akin to state functions.

 If a specific standard electrode is chosen, comparison to all other electrodes will result in a
practical system for determining cell potential.

Figure 7: Measurement of standard cell voltages for various combinations of the same half-reactions
suggests that a characteristic potential can be associated with a particular half-reaction.

Nonstandard Conditions

The cell potential at nonstandard conditions is calculated using the Nernst equation.
𝑅𝑇
𝐸 = 𝐸° − 𝑙𝑛𝑄
𝑛𝐹
Q is the reaction quotient, F is the Faraday constant, and n is the number of electrons transferred in the
reaction.

𝑎𝐴+𝑏𝐵 ↔ 𝑐𝐶+𝑑𝐷

[𝐶]𝑐 [𝐷]𝑑
𝑄=
[𝐴]𝑎 [𝐵]𝑏

F = 96,485 J V-1 mol-1 or 96,485 C mol-1

Problem 3

Assume that you have a cell that has an iron(II) concentration of 0.015 M and an H + concentration of 1.0
× 10-3 M. The cell temperature is 38°C, and the pressure of hydrogen gas is maintained at 0.04 atm. What
would the cell potential be under these conditions?

Application
Battery

A battery is an electrochemical cell which is used as the source of direct current of a constant voltage.

Battery

Primary (The cell Secondary (The cell Flow (The reactants, products and
reaction is not reaction is not reversible) electrolytes pass through the battery
reversible) and during the passage electric
current is generated at the expense
of chemical reactions as in
electrochemical cell
Electrolysis

Electrolysis is the process of passing an electric current through an ionic solution or molten salt to
produce a chemical reaction. Electrolytic cells are divided into two categories based on the nature of the
electrodes used.

 Passive electrolysis: the electrodes are chemically inert materials that simply provide a path for
electrons.
 Active electrolysis: the electrodes are part of the electrolytic reaction.

Electrolysis and Polarity

Electrolysis changes the polarity of the electrodes in a system. For reduction, electrons are forced to the
cathode. The cathode becomes the negative electrode. For oxidation, electrons are pulled from the anode.
The anode becomes the positive electrode.

Figure 12: In electrolysis, an external source of current drives a redox reaction that
would otherwise not be spontaneous. The flow of ions

Passive Electrolysis in Refining Aluminum

Electrolysis provides the means to overcome the nonspontaneous reaction to separate aluminum from its
oxide. The Hall-Heroult refining process uses carbon electrodes as inert sites for passive electrolysis.
 Figure 13: The Hall-Heroult process involves the electrolytic refining of
aluminum from Al2O3 to produce aluminum metal and oxygen gas.

Active Electrolysis and Electroplating

The process of depositing a thin coat of metal on another metal by using electrolysis is electroplating. In
some cases, the thin coating is cosmetic, or to provide some vital functionality for the coated piece, such
as corrosion resistance or desirable conductive properties. Silver is plated onto electrical devices because
silver is a good conductor and resistant to corrosion. The solution from which silver is plated contains
−
𝐶𝑁(𝑎𝑞) ions, which form a complex with 𝐴𝑔+ . The need for uniform coatings makes this an important
step. The object being electroplated is the cathode.

− −
Anode 𝐴𝑔(𝑠) + 2𝐶𝑁(𝑎𝑞) → 𝐴𝑔𝐶𝑁2(𝑎𝑞) + 𝑒−

−
Cathode 𝐴𝑔𝐶𝑁2(𝑎𝑞) + 𝑒 − → 𝐴𝑔(𝑠)

Opposite reactions at the anode and cathode are common for electroplating operations. Silver is
transferred from the anode to the cathode, coating the cathode in a thin layer of silver. The zero cell
potential is not critical since an external current drives electrolysis.

Electrolysis and Stoichiometry

For electroplating, it can be vitally important to use carefully controlled amounts of materials. Controlling
the flow of electrons (current) in an electroplating operation provides a method to accurately limit the
amount of material deposited. Electroplating is often used to prevent galvanic corrosion in an electrical
apparatus in places where different metals come into contact with one another.

Current and Charge

Using Faraday’s constant, F = 96,485 C mol -1 and the calculated charge, the number of moles of electrons
that pass through the circuit can be calculated. If the number of electrons required to reduce each metal
cation is known, the number of moles of material plated can be calculated.
Electricity use is often measured in terms of power. The SI unit for power is the watt (1 watt = 1 J s-1).
Electrical utilities normally determine consumption in kilowatt-hours, kWh (1 kWh = 3.60 × 106J).

Problem 4
In a process called flash electroplating, a current of 2.50 x 103 A passes through an electrolytic cell for
5.00 minutes. How many moles of electrons are driven through the cell?

Problem 5
Suppose that a batch of parts is plated with copper in an electrolytic bath running at 0.15 V and 15.0 A for
exactly 2 hours. What is the energy cost of this process if the electric utility charges the company $0.0500
per kWh?

Calculations Using Masses of Substances in Electrolysis

Knowledge of current, how long the current flows, stoichiometry, and the number of electrons required to
reduce a metal cation are used to answer the following questions. How much material is plated given a
specific current for an allotted time or electrical energy expenditure? How long must a given current to
pass through the cell to yield a desired mass of plated material?

Problem 6
An electrolysis cell that deposits gold (from Au+(aq)) operates for 15.0 minutes at a current of 2.30 A.
What mass of gold is deposited?

Problem 7
Suppose that you have a part that requires tin coating. You’ve calculated that you need to deposit 3.60 g
of tin to achieve an adequate coating. If your electrolysis cell (using Sn 2+) runs at 2.00 A, how long must
you operate the cell to obtain the desired coating?
 References

Brown L, Holme T. (2011). Chemistry for Engineering Students. Mary Finch.

https://ionlights.keybase.pub/books/Chemistry%20for%20Engineering%20Students%2C%202e.pdf

Jain J. (2015). Engineering Chemistry. Dhanpat Rai. https://pdfcoffee.com/engineering-chemistry-by-

jain-amp-jain-pdf-free.html