Lesson 1.

Electrochemistry
Outline
1.1. Oxidation-Reduction Reaction
1.2. Galvanic Cell
1.3. Cell Potential and Free Energy
1.4. Batteries and Fuel Cells
1.5. Electrolysis and Electroplating
1.6. Corrosion

Electrochemistry
Electrochemistry is the study of the relationship between electron flow and oxidation-reduction reactions or
termed as redox reactions. Applications of electrochemistry is numerous and important like in electrochemical
cells (commonly called batteries), electrolysis and electroplating. In electrochemical cells, electrons from
product-favored redox reactions are generated and transferred as an electrical current through an electrical
circuit. The voltage produced by an electrochemical cell depends on the oxidizing agent and reducing agents
used as reactants. However, not all product- favored redox reactions are beneficial, corrosion for example, is a
product- favored redox reaction but it results to damage to materials which is very costly.

On the other hand, electrolysis and electroplating are applications of redox reactions that are reactant-favored.
In an electrolysis cell, an external energy source causes an electric current to force a reactant-favored process to
occur. Electrolysis is important in the manufacture of many plated products like chrome plated objects.

This lesson discusses the basic principles of electrochemistry and its application.

1.1 Oxidation-Reduction Reaction

Oxidation-reduction reaction involves the transfer of electrons. Oxidation reaction is the loss of electrons from
a chemical species and reduction reaction is the gain of electrons. The overall redox reaction is a result of two
simultaneous half reactions: one half reaction for the oxidation and one-half reaction for reduction.

Example 1. Take for example Cu wire in a solution of AgNO3

(Source: Brown, WH & Holme, TA. (2011). Chemistry for Engineering Students, 2nd edition)

In beaker A, clean copper (Cu) wire is placed into a colorless solution of silver nitrate (AgNO3). In beaker
B, the color of the solution is changing to blue and silvery solids sticking on the wire appears. In beaker
C, as time passes, the solution turned blue and more silvery solids stick on the wire.
The blue color is an indication of the presence of copper ions (Cu 2+). The copper solid had been oxidized
producing copper ions. In the oxidization of copper solid, copper losses two electrons. The oxidation reaction
is:

Cu(s) →Cu 2+(aq) + 2e- oxidation reaction

The silvery solid sticking in the copper wire is silver (Ag). The silver cation (Ag +) in the solution of silver nitrate
(AgNO3) had been reduced producing silver solid. In the reduction of silver cation, silver cation accepts only one
electron. The reduction reaction is:

Ag+(aq) + 1e- → Ag(s) reduction reaction

The electrons can’t simply be lost. The electrons lost in the oxidation of a chemical species must always be
gained in the simultaneous reduction of another chemical species. We cannot have oxidation unless we also
have reduction. Hence, oxidation reaction and reduction reaction happen simultaneously.

The number of electrons lost or gained during oxidation and reduction reaction depends on the valence electrons
of the element. Valence electrons are the electrons in the highest energy level or outermost shell of the atom’s
electronic configuration. The valence electrons are like the group number where the element belongs in the
periodic table and this is true for the Group A elements.

The overall redox reaction for example 1 is:

Cu(s) → Cu 2+(aq) + 2e
Ag+(aq) + 1e- → Ag(s) * [2] (Ag is multiplied by 2 to balance the number of electrons)
Cu(s) → Cu 2+(aq) + 2e
2Ag+(aq) + 2e- → 2Ag(s)

Cu(s) + 2Ag+(aq) + 2e- → 2Ag(s) + Cu2+(aq) + 2e- (2e- cancels)

Cu(s) + 2Ag+(aq) → 2Ag(s) + Cu2+(aq) overall redox reaction

The overall reaction including the spectator ion (NO3– is the spectator ion) is:

2AgNO3 (aq) + Cu(s) → 2Ag(s) + Cu(NO3)2 (aq)

Silver ion (Ag+) oxidizes copper solid (Cu) and copper solid reduces silver ion. The species undergoing oxidation
is referred to as a reducing agent and the species undergoing reduction is referred to as oxidizing agent. Ions
are charged particles, a negatively charge ion is called anion and the positively charge ion is called cation.

Example 2. For the reaction: Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s)
a. Write the half reactions and label it as oxidation reaction or reduction reaction.
b. Determine the oxidizing agent and reducing agent.

Answers:
a. Half reactions
Zn(s) →Zn2+(aq) + 2e- Oxidation reaction
 Cu2+(aq) + 2e- → Cu(s) Reduction reaction

b. Zn(s) is the reducing agent

Cu2+(aq) is the oxidizing agent

1.2 Galvanic Cell

A galvanic cell is any electrochemical cell in which spontaneous chemical reaction can be used to generate an
electric current. The observation of electric current in an electrochemical cell led to the name electrochemistry,
this connects electricity and chemistry.

How could electricity be generated from a spontaneous chemical reaction? The oxidation and reduction reaction
presented in section 1.1 seems like an artificial idea because both oxidation and reduction reactions take place
in one container; the copper and silver are directly in contact. What would happen if the half reactions are in two
separate containers? Say for example copper in one container and silver in another container as shown in Figure
1.1 a.

Figure 1.1 A salt bridge is crucial in a galvanic cell

(Source: Brown, WH & Holme, TA. (2011). Chemistry for Engineering Students, 2nd edition)

In Figure 1.1a, copper solution is in one container and silver solution is in another container, no reaction occurs
because copper and silver are not in contact. Connecting the two solutions by a conducting wire, there will also
be no observable change because the wire cannot allow the flow of charge between the two solutions (copper
ion and silver ion cannot flow through the wire). Hence, there will only have a build-up of charges in the
electrodes. Electrodes are electrically conducting sites at which either oxidation and reduction takes place.
Oxidation occurs at the anode and reduction occurs at the cathode.

In Figure 1.1b, the two solutions relate to a salt bridge instead of a wire. The salt bridge allows migration of
cations and anions where they are needed. A salt bridge contains strong electrolytes that allows either cations
or anions to migrate into the solutions. Moving charges through the salt bridge closes the circuit, current can
flow and a cell voltage can be measured. This set up in Figure 1.1b is called a galvanic cell.

A galvanic cell has the following characteristics: a) half reactions are in different sites; b) a salt bridge is
inserted between the two solutions allowing flow of charges/electrons; and c) a sustainable electric current is
generated.
The shorthand method representing the electrochemical cell is called cell notation. The cell notation is written
as follows:

Anode │ Electrolyte of Anode ║ Electrolyte of Cathode │ Cathode

Example 3. The cell notation for the oxidation-reduction reaction of copper and silver is written
as: Cu(s) │ Cu 2+ (aq) ║ Ag+(aq)│ Ag(s)

Example 4. For the redox equation, Zn(s) + Cu2+ (aq) Zn2+(aq) + Cu(s), the cell notation is written as: Zn(s)│
Zn2+(aq)║ Cu2+(aq)│Cu(s)

1.3 Cell Potential and Free Energy

Cell Potential
The buildup of charges on the electrodes is important because it means that there is a potential for electrical
work. This potential is called cell potential. Measurement of cell potential is done using a voltmeter. The cell
potential is associated with a particular half reaction. All half-cell potentials are tabulated as standard reduction
potentials. A standard reduction potential shows the potential of any half reaction when connected to a SHE
(standard hydrogen electrode). Below are examples of standard reduction potentials of some half reactions.

Half Reaction Standard Reduction Potential (V) Zn 2+(aq) + 2e → Zn(s) - 0.763

Fe 2+(aq) + 2e Fe(s) - 0.44
2H+(aq) + 2e H2(g) 0.000
Cu 2+(aq) + 2e Cu(s) + 0.337
Fe 3+(aq) + e Fe 2+(aq) + 0.771
Ag+(aq) + e Ag(s) + 0.7794

Note that in the above examples of standard reduction potentials, all half reactions are written in a form of
reduction reactions. A voltage that is positive means the SHE is the anode or the oxidation site, hence, positive
voltage means that the half reaction proceeds as written (reduction). If the voltage is a negative value, the SHE
is serving as cathode or the reduction site, hence, the half reaction proceeds as oxidation.

The implications of the noted observations are: a) A large positive value for the standard reduction potential
implies that the substance is reduced readily and therefore a good oxidizing agent, reduction reaction occurs at
the cathode; b) A large negative value for the standard reduction potential implies that the substance is oxidized
readily and therefore a good reducing agent, oxidation reaction occurs at the anode.

The cell potential of a pair of half reactions is calculated as: E° cell = E° red – E° ox

Example 5. For copper and iron: Fe 2+(aq) + 2e- → Fe(s) E° = -0.44V

Cu 2+(aq) + 2e- → Cu(s) E° = 0.337V
a. Identify the anode and the cathode.
b. Determine the cell potential of the galvanic cell of copper and iron
c. Write the overall redox reaction.

Answers:
a. Fe 2+(aq) + 2e- →Fe(s) E° = -0.44V anode because the voltage is negative (oxidation)
Cu 2+(aq)+ 2e- → Cu(s) E° = 0.337V cathode because the voltage is positive (reduction)

b. Calculation of the cell potential

E° cell = E° red – E° ox
E° cell = 0.337V – (- 0.44V) = 0.78V

c. The overall redox reaction

Fe(s) → Fe2+(aq) + 2e- anode- oxidation reaction
Cu2+(aq) + 2e- → Cu(s) cathode-reduction reaction

Adding the half reactions, gives:

Fe(s) + Cu 2+(aq) + 2e- → Fe 2+(aq) + Cu(s) + 2e- (2e- cancel)

Fe(s) + Cu 2+(aq) → Fe 2+(aq) + Cu(s) overall redox reaction

Example 6. For copper and silver, confirm that the potential of the galvanic cell is
0.462V. Ag+(aq) + e- Ag(s) E° = 0.7994V
Cu2+(aq) + 2e- Cu(s) E° = 0.337V

Answers:
a. Ag+(aq) + e- Ag(s) E° = 0.7994V cathode because the voltage is largely positive (reduction)
Cu2+(aq) + 2e- Cu(s) E° = 0.337V anode because it is less positive (oxidation)

b. Calculation of the cell potential

E° cell = E° red – E° ox
E° cell = 0.7994V – (+0.337V) = 0.4624V

Free Energy
Free energy is the maximum work that can be done by a system. In a galvanic cell, this work done is the electrical
work. There is a relationship between free energy and cell potential and this relationship is defined in the
following equation: ΔG° = - nFE°

where: n = number of moles of e- (moles of electrons)

F = Faraday constant = 96,485 JV-1mol e-1
E° = cell potential
ΔG° = free energy or the Gibb’s free energy

The ΔG° is negative, because a galvanic cell has a positive potential and spontaneously generates electrical
work. The negative sign is required for a spontaneous process.

Example 7. For the galvanic cell of zinc and chromium: Cr(s)│ Cr2+ (aq)║ Zn2+(aq)│ Zn (s) a. Write the half
reactions and determine the anode and cathode or oxidation reaction and reduction reaction b. Determine
the E° cell c. Determine the ΔG°

Answers:
a. Half reactions
Cr(s) → Cr2+(aq) + 2e- anode (oxidation reaction)
 Zn2+(aq) + 2e- → Zn(s) cathode (reduction reaction)

b. Calculation of the E° cell

From the table of standard reduction potentials
Cr2+((aq) + 2e- → Cr(s) E = -0.910V anode (oxidation reaction)
Zn2+(aq) + 2e- → Zn(s) E = - 0.763 V cathode (reduction reaction)

E° cell = E° red – E° ox
E° cell = -0.763 – (-0.910) = 0.147 V

c. Calculation of ΔG°
ΔG° = - nFE°
ΔG° = - 2 mol e- * 96,485 JV-1mol e-1 * 0.147 V
ΔG° = - 2.84 x 104J

1.4 Batteries and Fuel cells

The electrochemical reactions provide opportunities for using it constructively like for example in the production
of batteries. A battery is a cell or series of cells that generates an electric current. Batteries are composed of
many different materials and has many uses. Batteries can be classified as primary cell or secondary cell.

Primary Cell
A primary cell is a single use battery that cannot be recharged. The most prevalent type of primary cell is alkaline
battery. The anode in the alkaline battery is zinc electrode and the cathode is derived from manganese (IV)
oxide. Figure 1.2 shows the essential design features of alkaline battery. The half reactions are as follows:

Anode: Zn(s) + 2OH-(aq) → Zn(OH)2 (s) + 2e

Cathode: 2MnO2(s) +H2O(l) + 2e- →Mn2O3(s) + 2OH-(aq)
Overall reaction: Zn(s) + 2MnO2(s) + 2H2O (l) → Zn(OH)2(s) + Mn2O3 (s)

Figure 1.2 Essential design features of a primary cell

(Source: Brown, WH & Holme, TA. (2011). Chemistry for Engineering Students, 2nd edition)

Primary cells have various applications. In some instances, the battery should be small and long-lasting like for
example batteries for medical devices. Mercury batteries fill this role. In a mercury battery, zinc is the anode and
mercury (II) oxide is the cathode. Figure 1.3 shows the design features of zinc-mercuric oxide battery. The half
reactions are as follows:

Anode: Zn(s) + 2OH-(aq) → Zn(OH)2(s) + 2e

Cathode: HgO(s) + H2O(l) + 2e- →Hg(l) + 2OH-(aq)
Overall reaction: Zn(s) + HgO(s) + H2O(l) →Zn(OH)2(s) + Hg(l)

Figure 1.3 Design features of zinc-mercuric oxide battery

(Source: Brown, WH & Holme, TA. (2011). Chemistry for Engineering Students, 2nd edition)

Secondary Cell
Secondary cell is a rechargeable battery. Secondary cells are very popular because of cellphones, digital
cameras, and computer devices like palmtop and laptop. An example of a secondary cell is nickel-cadmium
battery. In the nickel-cadmium battery, the anode is cadmium and the cathode is nickel. The half reactions are
as follows:

Anode: Cd(s) + 2OH-(aq) → Cd(OH)2(s) + 2e

Cathode: NiO(OH)(s) + H2O (l) + e- → Ni(OH)2 (s)+ OH-(aq)
Overall reaction: Cd(s) + 2NiO(OH) (s) + 2H2O (l) → Cd(OH)2 (s) + 2Ni(OH)2 (s)
The Ni-Cad batteries can be expended and recharged many times, but sometimes they are susceptible to a
performance decreasing memory effect. This memory effect involves the inability to use all the possible
chemical energy of the battery unless it is completely discharged. Successive recharging results in shorter times
before the battery appears to die. The chemistry that gives rise to this effect involves the formation of a thin
layer of material on the electrodes inside the battery, thus, limiting the oxidation-reduction reactions needed to
generate electrical work. Figure 1.4 shows the design features of Ni-Cad battery.

Figure 1.4 Design features of nickel-cadmium battery

(Source: Brown, WH & Holme, TA. (2011). Chemistry for Engineering Students, 2nd edition)

Fuel Cells
A fuel cell is a voltaic cell in which the reactants can be supplied continuously and the products of the cell reaction
are continuously removed. It uses a chemical reaction to produce electrical energy. It can also be refueled on an
on-going basis. The most common fuel cell is based on the reaction of hydrogen and oxygen to produce water.
Hydrogen flows into the anode compartment and oxygen gas flows into the cathode compartment. The
electrodes in each compartment are usually porous carbon which is impregnated with platinum catalyst. Oxygen
is reduced in the cathode and hydrogen is oxidized at the anode. The half reactions are as follows:
Anode: H2 → 2H+ + 2e
Cathode: O2 + 4H+ + 4e- → 2H2O
Overall reaction: 2H2 + O2 → 2H2O

Just like in any other voltaic cells, the half reactions are physically separated. Electrons flow from the anode to
the cathode through an external circuit, while protons pass through a special proton exchange membrane
separating the two electrode compartments. Fuel cells are used in a variety of specialized applications, including
powering instrumentation aboard spacecraft.

Limitations of Batteries
Battery manufacturing is a major industry and considerable researches are conducted to produce longer lasting,
better performing, or lighter batteries. The most common cause for the loss of performance of batteries is
corrosion. When you forgot to remove batteries from radio or flashlight that you did not use for months, it is
more likely that you will found the batteries to be corroded and possibly even allowing fluids to leak out of the
cells. To limit the performance-diminishing effects of corrosion on batteries, one method is the protective
plating of materials used in the battery by the process of electrolysis.

1.5 Electrolysis and Electroplating

Electrolysis
Electrolysis is a 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. If the
electrodes are chemically inert materials that simply provide a path for electrons, the process is called passive
electrolysis. Passive electrolysis is used in industry to purify metals that corrode easily. When the electrodes are
part of the electrolytic reaction, the process is called active electrolysis. Active electrolysis is used to plate
materials to provide resistance to corrosion.

Electroplating
Electroplating is a process of depositing a thin coat of metal by using electricity. Electroplating prevent
corrosion and is also vital to some functionality of coated piece. In electroplating, the important parameters to
investigate are: current; time; and amount of metal to coat.

Current: The base unit of current is Ampere (A); 1A = 1Cs-1

Charge: If a current pass through a circuit for a certain time the charge can be calculated
as Charge = current x time
Q=I*t
where: Q= charge (unit is Coulomb; C)
I = current (unit is ampere or Coulombs/second; C/s)
t = time (unit is seconds; s)

Example 8. In a process called flash electroplating, a current of 2.50 x103 A passes through an electrolytic cell
for 5 minutes. How many moles of electrons are driven through the cell?

Given: I = 2.50 x 103 A or 2.50 x 103 C/s

t = 5 min
Required: moles of e- driven to the cell.

Solution:
a. Solve for charge (Q)
Q=I*t
Q =2.50 x 103 A * (5 min * 60 s/1min)
Q = 2.50 x 103 C/s * 300 s
Q = 7.50 x 105 C

b. Solve for the moles e- driven to the cell using the Faraday constant (F = 96,485 JV-1mol e-
1
) Moles e- = Q / F
Moles e- = 7.50 x 105 C / 96, 485 JV-1 mol e-1
Moles e- = 7.50 x 105 C / 96,485 C mol e-1
Moles e- = 7.77 mol e

1J = 1CV
1J/V = 1C

Example 9. Suppose that a batch of parts is plated with copper in an electrolytic bath running at 0.15 V and 15
A at exactly 2 hours. What is the energy cost of this process if the electric utility charges the company P0.050
per KWh?

Given: Voltage = 0.15V Cost = P0.050/kWh

Current = 15 A or 15 C/s time = 2 hours
Required: Energy cost for the process

Solution:
a. Solve for charge (Q)
Q=I*t
Q = 15 C/s * (2 hr* 60 min/h * 60 s/min)
Q = 1.08 x 105 C

b. Solve for energy

E = Charge * Voltage
E = 1.08 x 105 C * 0.15 V
E = 1.08 x 105J/V * 0.15 V
E = 1.62 x 104J

c. Convert energy to KWh and determine cost

1kWh = 3.60 x 106J
1 watt = 1 Js-1

Energy cost = 1.62 x 104J * (1 kWh/ 3.60 x 106J) * P0.050/kWh

Energy cost = P 0.00023

Example 10. An electrolysis cell deposits gold from Au+(aq) and operates for 15 minutes at a current of 2.30 A.
What mass of gold is deposited?

Given: t = 15 minutes
I = 2.30 A
Required: amount of gold deposited (grams Au(s))

Solution:
a. Write a balanced half reaction for Au+(aq)
Au+(aq) + e- → Au(s)

b. Solve for charge (Q)

Q= I * t
Q = 2.30 C/s * (15 min*60 s/min)
Q = 2.070 x 103 C

c. Calculate moles of e- using Faraday constant

Moles e- = Q / F
Moles e- = 2.070 x 103 C / 96, 485 C mol e-1
Moles e- = 2.15 x 10-2 mol e

d. Calculate moles Au(s) using mole ratio

From the balanced half reaction in letter a, 1 mole of e- produces 1 mole Au(s)
Moles Au(s) = moles e- * mole ratio
10
-2
Moles Au(s) = 2.15 x 10 mol e- * 1 mol Au(s)/ 1 mol e
Moles Au(s) = 2.15 x 10-2 mol Au(s)

e. Convert mole Au(s) to grams using the formula weight

Grams Au(s) = moles Au(s) * Formula weight of Au(s)
Grams Au(s) = 2.15 x 10-2 mol Au(s) * 197 g/mol
Grams Au(s) = 4.23 g Au(s)

1.6 Corrosion
Corrosion is the degradation of metals by chemical reaction with the environment. It generally involves a slow
combination of oxygen and water with metals to form compounds called oxides or hydrated oxides. Corrosion
is an example of an electrochemical process, but corrosion alone does not define electrochemistry. Rusting or
corrosion is seen to be disastrous. It causes accidents in industry, on highways, and in homes. It is wasteful
financially costing industrialized nations 4-5% of their gross domestic products annually.

Metals differ in its behavior towards corrosion, how fast a metal corrodes depends on its reactivity. More reactive
metals corrode faster than less reactive metals. But corrosion behavior between aluminum and iron is different.
Aluminum has greater tendency to corrode because it is more reactive than iron, but corrosion of aluminum is
less problematic than iron. This difference in corrosion behavior of aluminum and iron lies in the nature of the
products of corrosion reaction. Aluminum oxide (Al2O3), the product of corrosion of aluminum is less
problematic because it is very unreactive, it sticks tightly to the surface of the metal serving as a protective layer
such that no cracks are formed preventing further corrosion.

Corrosion occurs in a variety of forms. The most common visible form of corrosion is uniform corrosion which
rusting of automobile bodies is an example. Another important form of corrosion is galvanic corrosion, which
occurs when two different metals are in contact to each other in the presence of an appropriate electrolyte.
Another form is crevice corrosion which is a major problem in many large machines, this happens when two
pieces of metal touch each other but tend to leave a small gap. At this gap or crevice, the metals are more likely
to corrode unless the joint is covered with a coating. Other forms of corrosion require specific conditions and
many of these situations are common in designs of machinery.

Corrosion results to great economic loss, hence, corrosion control is very important. The most common means
of protecting a material from corrosion is coating the more reactive metal with less reactive metal. This process
is called galvanizing or the metal is plated, it undergoes a process called electroplating. Another widely used
coating practice is painting. Paint coatings protect the material from exposure to water and oxygen.

Cathodic protection is also a means of protecting a metal from corrosion. Cathodic protection is a process of
creating a galvanic corrosion condition where the material that easily rusts is made as the cathode by connecting
it electrically to a more reactive metal that serves as the sacrificial anode (Figure 1.5). Corrosion of iron, for
example, can be prevented by choosing magnesium as the sacrificial anode that is connected electrically to the
iron. Since, magnesium has a reduction potential that is more negative than iron, the magnesium is oxidized and
the iron is reduced. The iron is made as the cathode and magnesium is the anode. Using sacrificial anode is one
effective method of corrosion prevention.

Iron pipe (cathode) Magnesium (sacrificial anode) Figure 1.5 Cathodic protection

References
1. Brown, WH & Holme, TA. (2011). Chemistry for Engineering Students. 2nd edition, Brooks/Cole, Centage
Learning, USA.
2. Gaffney J & Marley N. (2017). General Chemistry for Engineers. 1st edition, Elsevier Publishing. 3. Moore,
JW, Stanitski, CL & Jurs, PC. (2005). Chemistry: The Molecular Science. 2nd edition, Brooks/Cole, Thomson
learning, Canada.
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