University of Science and Technology of Southern Philippines

Cagayan de Oro City

1st Semester SY 2022-2023
 2

TOPIC 6: Electrochemistry
OUTLINE
VI. Electrochemistry

•Insight into Corrosion

•Oxidation-Reduction Reactions and Galvanic cells
•Cell potentials
•Cell Potentials and Equilibrium
•Batteries
•Electrolysis
•Electrolysis and Stoichiometry
•Insight into Corrosion Prevention
3
LEARNING OUTCOMES
•Describe at least three types of corrosion and identify chemical reactions responsible for
corrosion;
•Define oxidation and reduction;
•Write and balance half-reactions for simple redox processes;
•Describe the differences between galvanic and electrolytic cells;
•Use standard reduction potentials to calculate cell potentials under both standard and
nonstandard conditions;
•Use standard reduction potentials to predict the spontaneous direction of a redox reaction;
•Calculate the amount of metal plated, the amount of current needed, or the time required for
an electrolysis process;
•Distinguish between primary and secondary batteries;
•Describe the chemistry of some common battery types and explain why each type of battery os
suitable for a particular application; and
•Describe at least three common techniques for preventing corrosion. 4
5
6
 7

Corrosion
• Corrosion is the degradation of metals by chemical reactions
with the environment.
• Uniform corrosion occurs evenly over a large portion of the
surface area of a metal.
• Galvanic corrosion occurs when two different metals contact
each other in the presence of an appropriate electrolyte.
• Crevice corrosion occurs when two pieces of metal touch each
other, leaving a small gap or crevice between the metals.
8
 9

Corrosion
• Different metals corrode differently.
• 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.
• The iron oxide corrosion product flakes off the surface of
iron, exposing fresh iron to corrosion.
 10

Corrosion

Corrosion occurs in a variety of forms. The chain shows uniform corrosion.

The grill cover shows crevice corrosion where the handle is attached.
 11

Oxidation-Reduction Reactions and Galvanic Cells

• Special conditions must be present before iron reacts with
oxygen to form iron(III) oxide.
• Rust formation is a slow process, so the basics of electrochemistry
must be investigated using more easily observed reactions.

• Reactions that transfer electrons between reactants are known

as oxidation-reduction or redox reactions.
• Oxidation is the loss of electrons from some chemical species.
• Reduction is the gain of electrons to some chemical species.
 12

Oxidation-Reduction and Half-Reactions

• For an oxidation-reduction reaction to occur, one reactant
must be oxidized and one reactant must be reduced.
• Oxidation cannot occur without reduction.

• 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.
 13
Oxidation-Reduction and Half-Reactions

• When a clean copper wire is placed into a colorless solution of silver

nitrate, it is quickly apparent that a chemical reaction occurs.
 14

Oxidation-Reduction and Half-Reactions

• 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 is oxidized.

• The crystals forming on the surface of the copper wire are silver
metal.
• Silver is formed when a silver cation gains an electron.
• The silver cation is reduced.
 15

Oxidation-Reduction and Half-Reactions

• 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.
 16

Oxidation-Reduction and Half-Reactions

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

_____________________________________
 17

Oxidation-Reduction and Half-Reactions

• The species undergoing oxidation is referred to as a reducing
agent.
• The Cu was oxidized and is the reducing agent.
• The Cu facilitated the reduction of Ag+ by losing electrons.

• The species undergoing reduction is referred to as an oxidizing

agent.
• The Ag+ was reduced and is the oxidizing agent.
• The Ag + facilitated the oxidation of Cu by gaining electrons.
 18

Building a Galvanic Cell

• 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.
 19

Building a Galvanic Cell

• 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.
 20

Building a Galvanic Cell

A salt bridge is crucial to a galvanic cell. The salt bridge allows ions to
flow between each half-cell, completing the circuit.
 21

Terminology for Galvanic Cells

• 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.

• Cell notation - 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.
 22

Terminology for Galvanic Cells

• General form of cell notation

• For the previous example of copper and silver

• The electrolyte concentration is also given.

• An electrochemical cell is at its standard state when the electrolyte

concentrations are 1 M.
• For half-cells that generate or consume a gas, a partial pressure of 1
atm is required for the standard state.
 23

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.
 24

Atomic Perspective on Galvanic Cells

• Without a salt bridge to close

the circuit, local charges build
up around both electrodes.
Neither electrode reaction can
proceed to any significant
extent, so no cell voltage can be
measured.
 25

Galvanic Corrosion and Uniform Corrosion

• Metals in contact with a solution establish an 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 a 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.
 26

Galvanic Corrosion and Uniform Corrosion

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.
 27

Galvanic Corrosion and Uniform Corrosion

• 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.
 28

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.
 29

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.

• 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.
 30

Measuring Cell Potential

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.
 31

Measuring Cell Potential

• 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 H2 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.
 32

Measuring Cell Potential

• For the Standard Hydrogen Electrode

• The half-reaction for the SHE is: 2 H+(aq) + 2 e– → H2(g).

• The half-cell notation is: Pt(s) | H2 (g, 1 atm) | H+ (1 M).

• The half-cell is assigned a potential of exactly zero volts.

• The cell potential is attributed to the other half-reaction.

 33

Measuring Cell Potential

• For some galvanic cells, the SHE acts as the anode and for other
galvanic cells, the SHE acts as the cathode.
• The anode is the site of oxidation, releasing electrons and creating a
negatively charged electrode.
• If the anode is connected to the positive terminal of the voltmeter, a
negative potential is measured.

• The cathode is the side of reduction, consuming electrons and

creating a positively charged electrode.
• If the cathode is connected to the positive terminal of the voltmeter, a
positive potential is measured.
 34

Measuring Cell Potential

• When the SHE is always connected to the positive terminal, the sign
of the potential tells us the direction of the redox reaction.

• When the potential is negative, the SHE is the anode, and H2 is oxidized
to H+(aq).
• When the potential is positive, the SHE is the cathode, and H+ (aq) is
reduced to H2.
 35

Measuring Cell Potential

Just like a commercial battery, a galvanic cell has a fixed polarity. Electrons flow through
the external circuit from the anode to the cathode. Reversing the leads of the voltmeter
changes the sign of the reading, but does not influence the flow of current.
 36

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.
• All materials are 1 M for aqueous species and 1 atm partial pressure
for gases.
 37

Standard Reduction Potentials

Standard reduction potentials for several half-reactions involved in the

cells discussed in the text.
 38

Standard Reduction Potentials

• 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.
 39

Standard Reduction Potentials

• All potentials are measured with a SHE connected to the negative
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.
 40

Standard Reduction Potentials

• 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.
 41

Standard Reduction Potentials

• 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.

• E˚red is the standard reduction potential for the cathode

• E˚ox is the standard reduction potential for the anode.
 42

Standard Reduction Potentials

For standard reduction potentials arranged horizontally, the anode and cathode
for a galvanic cell can easily be determined. The reduction potential furthest to
the left is the anode.
 43

Example Problem 1:
PROBLEM: Copper and iron (generally in the form of steel) are two of the
many metals used in designing machines. (a) Using standard
reduction potentials, identify the anode and the cathode and
determine the cell potential for a galvanic cell composed of copper
and iron. Assume standard conditions. ( b) We can also construct a
galvanic cell using copper and silver. Confirm that the potential of
the following galvanic cell is 0.462 V:
 44

Example Problem 1:
SOLUTION: (a) Using Table (Slide #32), we find the following two half-reactions

Iron must be oxidized for a combination of these two half-reactions

to yield a positive cell potential:

Copper is the cathode in this cell because copper is reduced; iron is

the anode because it is oxidized.
 45

Example Problem 1:
SOLUTION: (a) (b) Find the two half-reactions in Table (Slide #32), we find the
following two half-reactions

From the values of the standard reduction potentials, we can see

that copper is oxidized, and silver is reduced. To find the cell
potential:
 46

Nonstandard Conditions

• The cell potential at nonstandard conditions is calculated using

the Nernst equation.

• Q is the reaction quotient, F is the Faraday constant, and n is the

number of electrons transferred in the reaction.
• F = 96,485 J V-1 mol-1 or 96,485 C mol-1

• Thus for the generic reaction

 47

Example Problem 2:
PROBLEM: Suppose that you work for a company that designs the drive
mechanisms for large ships. The materials in this mechanism will
obviously come into contact with environments that enhance
corrosion. To estimate the difficulties that corrosion might cause,
you decide to build a model electrochemical cell using electrolyte
concentrations that might be present in your system when it is in
service. Assume that you have a cell that has an iron(II)
concentration of 0.015 M and an H+ concentration of 1.0 x 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?
 48

Example Problem 2:
SOLUTION:

These reactions tell us two things: first, the standard cell potential
will be
 49

Example Problem 2:
SOLUTION: Second, there are two electrons transferred in the overall redox
reaction:

These facts, plus the values given in the problem and those of the
constants allow us to use the Nernst equation to find the cell
potential:
 50

Cell Potentials and Free Energy

• Under standard conditions the maximum cell potential (E°) is directly
related to the free energy (G) difference between the reactants and the
products.

• This equation allows us to test for ∆G° in the lab.

∆G° = - nFE°
G = Gibbs free energy kJ/mol
n = moles of e- exchanged
F = Faraday’s constant 96,500 coulombs/mole
(how much charge is produced for every 1 mole of e- )
E° = Standard reduction potential
 51

Example Problem 3:
PROBLEM: Suppose that we wish to study the possible galvanic corrosion
between zinc and chromium, so we set up the following cell:

What is the chemical reaction that takes place, and what is the
standard free energy change for that reaction?

SOLUTION:
 52

Equilibrium Constants
• ΔG° is related to the equilibrium constant, K

• At equilibrium, the free energy change is zero and the reaction quotient,
Q, is equal to the equilibrium constant, K.

• The factor of 2.303 is the result of changing from the natural log to the common log
function: ln (10) = 2.303.
 53

Equilibrium Constants

• R and F are constants

• At the standard temperature of 25°C (298 K)

• An electrochemical reaction that transfers only one electron at a potential

of 1.0 V, the value of K can be determined, obtaining:
 54

Equilibrium Constants

The variation of equilibrium constant with cell potential is shown. The

different lines correspond to reactions involving the transfer of one, two,
or three electrons, as indicated.
 55

Batteries
• A battery is a galvanic cell
or, more commonly, a
group of galvanic cells
connected in series.

• A battery is a cell or series

of cells that generates an
electric current.

• Batteries are susceptible

to corrosion
 56

Primary Cells
• Single-use batteries that cannot be recharged are called primary cells or
primary batteries.
• The most prevalent type of primary battery in use today is the alkaline
battery.
• The anode in an alkaline battery is a zinc electrode, and the oxidation half-
reaction can be written:

• The cathode is derived from manganese(IV) oxide, and the half-reaction is

• Combine these two half-reactions to yield a net equation that represents

the chemistry of an alkaline dry cell battery.
 57

Primary Cells

• Anode:

• Cathode:

Construction of a typical alkaline battery

 58

Primary Cells

• Anode:

• Cathode:

• The mercury battery (also called a zinc-mercuric oxide cell) shown here has a voltage
output that is extremely stable over long times. These batteries are commonly used in
devices where frequent battery changes would be a nuisance or hazard.
 59

Primary Cells
• Anode:

• Cathode:

• In a zinc-air battery, one of the reactants is oxygen from the surrounding air. As a result,
these batteries can offer a very attractive energy density. They can also be kept on hand
in sealed bags and charged when needed by opening the bag to expose the battery to air.
 60

Secondary Cells
• Rechargeable batteries represent examples of secondary cells or secondary
batteries.

• Anode:

• Cathode:

Nickel-Cadmium Battery
 61

Secondary Cells
• Anode:

• Cathode:

Nickel-metal-hydride batteries
 62

Secondary Cells
• Anode:

• Cathode:

Lead-acid storage battery

 63

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.
• The most common fuel cells are based on the reaction of hydrogen and
oxygen to produce water.
• Anode:

• Cathode:

• Over-all cell reaction:

 64

Electrolysis
• Electrolysis is the process of passing an electric current through an
ionic solution or molten salt to produce a chemical reaction.
• If the electrodes are chemically inert materials that simply provide a
path for electrons, the process is called passive electrolysis.
• Used in industry to purify metals that corrode easily.

• When the electrodes are part of the electrolytic reaction, the process is
active electrolysis.
• Used to plate materials to provide resistance to corrosion.
 65

Electrolysis and Polarity

• Electrolysis changes the polarity of the electrodes in a system.
• In electrolysis, an external source of current drives a redox reaction that
would otherwise not be spontaneous.
 66

Passive Electrolysis in Refining Aluminum

• The Hall-Heroult process involves the electrolytic refining of aluminum from Al2O3.
• Carrying out the electrolysis in a bath of cryolite (Na3AlF6) lowers the required
temperature significantly, making the process economically feasible.
 67

Active Electrolysis and Electroplating

• The process of depositing a thin coat of metal by using electricity is
called electroplating.
• e.g. Plating of silver to make parts for electrical devices:

• Anode:

• Cathode:
 68

Active Electrolysis and Electroplating

• Barrel plating is often used to apply coatings to small parts.

• The barrel cathode rotates during electrolysis to ensure that all parts come into
contact with the electrode
 69

Electrolysis and Stoichiometry

• Current and Charge
• If a known current passes through a circuit for a known time, the
charge can be easily calculated.

where: Q in coulombs
I in amperes (coulombs/second)
t in seconds
 70

Example Problem 4:
PROBLEM: 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?
 71

Example Problem 4:
PROBLEM: 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?

SOLUTION:

Use Faraday’s constant:

 72

Example Problem 5:
PROBLEM: 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?
 73

Example Problem 5:
PROBLEM: 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?

SOLUTION:

Convert to kWh and determine the cost:

Note: ;
 74

Example Problem 6:
PROBLEM: 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?
 75

Example Problem 6:
PROBLEM: 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?

SOLUTION: 1) Write the balanced half-reaction:

2) Calculate moles of electrons based on current and time:

3) Note that the mole ratio of electrons to gold is 1:1, which means
that we also have 2.15 x 10-2 mol of Au.
 76

Example Problem 7:
PROBLEM: Suppose that you have a part that requires a 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 Sn2+) runs at 2.00
A, how long must you operate the cell to obtain the desired
coating?

SOLUTION:
 77

Corrosion Prevention
• The following observations can be used to reduce corrosion in a
number of ways.
• Corrosion is a pervasive reaction, with a large, negative free energy
change.
• It is possible to predict what materials will corrode and use this
information to protect a material such as iron.
• Some materials, like aluminum, corrode readily, but the product, in this
case Al2O3, forms a protective layer that eliminates further corrosion.
 78

Coatings
• Applying a protective coating to a material is the most common
way of protecting against corrosion.

• A coating can be applied with electroplating or painting.

• The coating protects the underlying material from exposure to

water and oxygen.
 79

Cathodic Protection
• Some materials are more easily oxidized than iron, which provides a way
to construct galvanic corrosion conditions intended to protect the iron.
• Mg has a reduction potential more negative than Fe.
• When combined, Mg will oxidize and Fe will be reduced.

• Magnesium can be used to prevent iron corrosion.

• The piece of magnesium is called a sacrificial anode.
• Connecting magnesium to iron forces iron to be the cathode, preventing
iron from oxidizing.
• This process is called cathodic protection.
• The sacrificial anode must be replaced periodically to be effective.
 80

Cathodic Protection

• Sacrificial anodes are one effective method of corrosion prevention. The anode is
preferentially oxidized relative to the protected metal.
 81

Preventing Corrosion in space

• Corrosion prevention is a concern for NASA.
• Corrosion prevention at the launch site is a major concern.
• Batteries used in the International Space Station (ISS) must be
prevented from corroding in the ISS’s earth-like atmosphere.
• The corrosivity of a planet’s atmosphere must be known before a
craft can land safely.
OUTLINE
VI. Electrochemistry

Insight into Corrosion

Oxidation-Reduction Reactions and Galvanic cells
Cell potentials
Cell Potentials and Equilibrium
Batteries
Electrolysis
Electrolysis and Stoichiometry
Insight into Corrosion Prevention
82
LEARNING OUTCOMES
Describe at least three types of corrosion and identify chemical reactions responsible for
corrosion;
Define oxidation and reduction;
Write and balance half-reactions for simple redox processes;
Describe the differences between galvanic and electrolytic cells;
Use standard reduction potentials to calculate cell potentials under both standard and
nonstandard conditions;
Use standard reduction potentials to predict the spontaneous direction of a redox reaction;
Calculate the amount of metal plated, the amount of current needed, or the time required for
an electrolysis process;
Distinguish between primary and secondary batteries;
Describe the chemistry of some common battery types and explain why each type of battery is
suitable for a particular application; and
Describe at least three common techniques for preventing corrosion. 83
 84

PRIMARY REFERENCE
L. S. Brown & T. A. Holme. Chemistry for Engineering Students.

OTHER REFERENCES
W.L. Masterton & C. N. Hurley. Chemistry :Principles and Reactions.

M.S. Silberberg. Chemistry: The Molecular Nature of Matter and Change.

T.L. Brown, et. al. Chemistry: T h e C e n t r a l S c i e n c e.

M. S. Silberberg. Principles of General Chemistry.

R. Chang. Chemistry.