13.

Electrochemistry

1.Corrosion
2.Oxidation -Reduction Reactions and
Galvanic Cells
3.Cell Potentials
4.Cell Potentials and Equilibrium
5.Batteries
6.Electrolysis
7.Electrolysis and Stoichiometry
8.Batteries in Engineering Design

Dr.Phyu Phyu Zan (AP)

1.Corrosion

• Corrosion generally involves a slow combination of oxygen with

metals to form oxides.
• Researchers have identified many different forms of corrosion.
• Rusting of automobile bodies is an example of uniform corrosion and
is one of the most visible forms of corrosion.
• Another important form of corrosion is galvanic corrosion, which
occurs only when two different metals contact each other in the
presence of an appropriate electrolyte.
• Crevice corrosion is a major problem in many large machines. When
two pieces of metal touch each other, to leave a small gap (joint is
covered with a coating ,such as paint).
• Gap or crevice, the metals are more likely to corrode.
• Corrosion is the difference between iron (or steel) and other metals in
their behaviour . For example,Aluminium has a greater tendency to
corrode than iron, but the corrosion of aluminium is not problematic.
 2. Oxidation-Reduction Reaction and Galvanic Cells

• Reactions involving the transfer of electrons are known as oxidation

reduction reactions (redox reaction).
• Oxidation is the loss of electrons from some chemical species,
whereas reduction is the gain of electrons.
• Copper wire in a solution of silver nitrate (Fig 13.2).Original solution
silver nitrate is clear and colourless and copper wire is smooth. A
short time after the wire is placed in the solution, copper wire looks
fuzzy and the solution becomes light blue. In the final photo, Buildup
silvers of silver metal on the wire and the solution is distinctly blue.
What has happened chemically ?
• Forming cations, copper atoms must have lost electrons. Copper
has been oxidised.Silver cation in solution have accepted the
electrons lost by copper. Silver has been reduced and again.
• Two equations are called half reactions for the oxidation copper and
the reduction of silver.Net ionic equation for the overall redox
reaction; ……….
Building a Galvanic Cell
• A galvanic cell is any electrochemical cell
in which a spontaneous chemical reaction
can be used to generate an electric
current.
• The observation of an electric current in
such a cell led to the name
electrochemistry.
• A salt bridge contains a strong electrolyte
that allow either cation or anions to
migrate into the solution where are needed
to maintain charge neutrality.
• Salt bridge is filled with NH4Cl. Ammonium
ions will flow into the beaker of silver
solution to offset the removal of Ag+ and
chloride ions will flow into the beaker of
copper solution to offset the production
Cu2+ in copper solution beaker.
Terminology for Galvanic cells

• Electrically conducting site at which either oxidation or reduction

take place are called electrodes.
• Oxidation occurs at the anode and reduction occurs at the cathode.
• Cell notation ;
• Anode/Electrolyte of anode//Electrolyte of cathode/Cathode
• Standard state (Concentration of 1M, Pressure of 1atm)
Atomic Perspective on Galvanic Cell

• Atomic
• Equilibrium state at each electrode the half reaction equilibrium but
it is not an oxidation reduction equilibrium.
• The buildup of charge on the electrode is important because it
means that a potential for electrical work. This potential is called the
cell potentials or electromotive force (EMF).EMF is related to the
maximum electrical work that can be obtained from an
electrochemical cell.
• Wmax =qE
Galvanic corrosion and Uniform corrosion
• Two metals are in contact, there is possibility of galvanic
corrosion.The process is similar to a galvanic cell in the oxidation
and reduction take place in different locations but there is a
connection of the metals that completes the circuit.
• Tin is mostly steel, usually the steel is plated with tin. If scratch in
the tin and underlying steel is exposed to air and water. Corrosion
will be rapidly.
• Because the half-reaction equilibrium of the tin assists the process
by which iron is oxidised.
• Pure steel will corrode more slowly, and zinc plated steel will
corrode even more slowly.
• In uniform corrosion, rust can cover the surface of iron or steel. The
second electrode is a second region of the iron itself, located some
distance away from the first spot.
3. Cell Potentials
Measuring Cell Potential
• Result depends on which terminal on the voltmeter is attached to which
electrode.
• Voltmeter measures the size of the electrode potential and also its
polarity; the location of the negative charge (negative pole) and the
positive charge (positive pole).
• Example of copper and silver;Cell potential of 0.462 V.
• Two reasons; First shows a behaviour of cell potential is akin to the state
function. Second chooses a specific standard electrode which compare
all other electrode and devise a practical system for determining cell
potential.
The positive terminal of
the meter is connected
with a red wire and the
negative with a black wire.
Fig.7 An electric potential
has a fixed polarity and
voltage.
• Standard hydrogen electrodes (SHE, Cell potentials =0 Volt )

• To determine exactly zero volts of SHE- Always connecting the SHE to the
positive terminal of the voltmeter when other electrodes are attached to
the negative terminal of the voltmeter, both positive and negative values
are observed.
• Anode is the site of oxidation, so electrons are released there. Anode has
negative charge in galvanic cells.
• Half cell notation; pt/ H2 (1atm)/ H+(1M)
• Measure cell potential is positive, SHE is anode,
• H2 is oxidized to H+.
• Cell potential is negative, SHE is the cathode,
• H+ is reduced to H2.
Standard Reduction
Potential
• In any galvanic cell, the half reaction
the more positive reduction potential
will be cathode.
 Example 1.

Copper and iron 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 potentials 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 potentials of the following galvanic cell is
0.462 V.
Cu/Cu2+(1M) // Ag+(1M)/Ag
Solution; (a)

Example 2 and 3
Cathodic protection

• Magnesium reduction potential is more negative than that of iron.

Magnesium is oxidised and iron is reduced.
• To prevent iron from corroding, use a piece of magnesium as a
sacrificial anode.
• Connecting the piece of magnesium to the iron forces to be cathode,
preventing the oxidation of iron. The process is called CP.
• By making the iron a cathode, it cannot be anode and will not be
corrode.
• To be effective, sacrificial anode must be replaced periodically and
used, including the protection of iron or steel pipelines.
Nonstandard conditions
4.Cell potentials and Equilibrium

Cell potentials and Free Energy

• Free energy is related to the maximum possible amount of work that

can be done by the system.
• In galvanic cells, the work done is electrical work so the relationship
between free energy and cell potential as

Galvanic cell always has a positive cell potential. Cell reaction is

spontaneous, so free energy must be negative. Example problem, 13.3
 Insight; Iron is initially oxidised. Oxygen dissolved in the water undergoes the
reduction.

Equilibrium constants
 5.Batteries

• Battery, a cell or series of cells that generate an electrical

current. Batteries are composed of many different materials
and many uses.
• Batteries are sometimes classified as either primary or
secondary.
• Primary cell such as the typical alkaline battery becomes
useless once the underlying chemical reaction has run its
course.
• Secondary cell is one that can recharge, allowing for a much
longer life cycle.
• To make a recharge battery, able reverse the redox reaction,
converting the product back into reactants. Because the cell
reaction must be exothermic to supply energy. Reverse
reaction must be endothermic.
Primary Cells (Dry cell)

• Primary battery in use today is the alkaline battery. Flashlight , many toys,
radios and other devices.
• Anode in alkaline battery is zinc electrode,
• Cathode is manganese IV oxide,
• Alkaline dry cell battery;
• Electrolyte use is KOH, but rather than dissolving the electrolyte in liquid
water, it is a form of a paste or gel (dry cell)
• MnO2 for the cathode is mixed with graphite to increase conductivity.
• Anode is a paste containing powdered zinc.
Other primary cells

• For a medical device, such as a heart pacemaker

• Lithium batteries
• Lithium metal is the anode
• Cathode uses manganese (IV) oxide reacts with Lithium
ions.
• Electrolyte is a lithium salt dissolved in an organic
solvent which can diffuse through the polypropylene
separator.
• Znic air batteries are sold
as single use, long lasting
products for emergency
use in cellular phones.
• The anode reactions
involve the oxidation of
zinc.
• At the cathode, oxygen
from the air is reduced
 Secondary cells
• Rechargeable batteries are increasingly common in consumer products.
• Nickel metal hydride batteries are available in many standard sizes and
can be used to replace alkaline batteries in most applications .
• Lager versions serve as the main batteries in many hybrid cars, including
the Toyota Prius.
Lead-acid storage batteries

• Anode and cathode reaction

• Electrolyte for this battery is sulphuric acid
• Cell designated by the reaction given above generates a
potential of nearly 2.0V.
• Standard 12 V automobile battery, need six cells in series.
• Batteries are rechargeable-
• Passing electric current to drive the redox reaction in the
non spontaneous direction recharges the battery.
Fuel cells
• Fuel cell is voltaic cell
• Like battery, uses a chemical reaction to produce electrical energy.
• Unlike a battery, it can be refuelled on ongoing basis.
• Fuel cells are based on the reaction of hydrogen and oxygen to produce
water.Hydrogen gas flows into the anode compartment and Oxygen gas
flows into the cathode compartment.
• Electrodes in each compartment are usually porous carbon.
• Oxygen is reduced at the cathode
• Hydrogen is oxidised at the anode
• Electrons flow from the anode to cathode through an external circuit ,
While protons pass through a special proton exchange membrane
separating the two electrode components.
• Fuel cells using alternate fuel such as methanol or methane rather then
hydrogen are also being explored.
 6.Electrolysis
• Electrolysis is the process of passing an electric current
through an ionic solution or molten salt to produce a chemical
reaction.
• Two categories based on the nature of the electrode used.
• If the electrode are chemically inert materials that simply
provide a path for electrons, the process is called passive
electrolysis.When the electrodes are part of the electrolyte
reaction, active electrolysis.
• Passive electrolysis is used in industry to purify metals that
corrode easily.
• Active electrolysis is used to plate materials to provide
resistance to corrosion.
 Electrolysis and Polarity
• Electrolysis changes the polarity of the electrodes in a system.
• Instead of the reaction occurs spontaneous at the electrodes, the
external power supply causes the reverse reaction to occur.
• For reduction, electrons are forced to the cathode in an electrolytic
reaction.
• Cathode is still the site of reduction, but in electrolysis it is negatively
charged because the external power supply forces electrons to the
location of the reaction.
• Anode is still the site of oxidation, but in electrolysis it is positively
charged, the external power supply pulls the electrons away from the
region of the oxidation reaction.
 Passive Electrolysis in Refining Aluminium

• Aluminium does not corrode.Pure aluminium metal reacts with oxygen very
quickly. When this corrosion occurs, a thin layer of Al2O3 is formed at the
surface of the metal.
• The oxide surface is strongly bonded to the pure aluminium underneath
protects and makes it useful in a variety of applications.
• Formation of Al2O3 can be predicted from the standard reduction potential
of Al/Al3+ half reaction. With E= -1.66 V, aluminium is a considerably
stronger reducing agent than iron, Fe/Fe2+ , E = -0.44V.
• If the reaction to from aluminium ions is thermodynamically favourable,
the reverse reaction will not be spontaneous. (The refining of aluminium
from ore)
• Electrolysis provides the non spontaneous reaction to separate aluminium
from oxygen.
• Hall-Heroult process uses carbon electrodes as inert sites for passive
electrolysis.
• Three components of this process are important its usefulness.
• First is the inclusion of Na3AlF6 or cryolite in the reactor, which lowers the
melting point from 2045 C for the mixture.
• Lower temperatures can be achieved more readily and make refining
aluminium economically viable.
• Second, the process requires larger amounts of electric current to produce
substantial amounts of aluminium.
• Amounts of electricity become available from large hydroelectric project in
the 20th century.
• Finally, the precise reaction are not known, the electrolytic reactions
ultimately produce oxygen gas.
• Adds additional cost to the production of aluminium because the oxygen
reacts slowly with the carbon in the graphite rods to form carbon dioxide.
• The destruction of the graphic electrodes over time means replace
regularly.
• Aluminium is familiar material in everyday life because electrolysis of
aluminium containing ore is both possible and economically
viable.Because electricity requirement for this process, recycling of
aluminium is less expensive than the recovery of aluminium from its ore.
• Recycling one aluminium can save enough electricity to light a 100 watt
bulb which can study chemistry for 4 hours.
 Active Electrolysis and Electroplating

• The process of depositing a thin coat of metal by using electricity is called

electroplating.
• Electron collector that provides the external connection for the anode is
electroplated.
• Metal coating gives this piece of material a battery both corrosion protection
and desirable conducting properties.
• Small parts are plated in bulk by placing them in a barrel and the barrel in the
electrolysis solution.
• Solution from which silver is plated normally contains cyanide ions, which
form complexes with silver.
• For uniform coating makes this step important. The anode and cathode
reaction; …………
• The barrel is rotated during the plating process so that all the small parts it
contains electrical contact with the cathode, becoming part of cathode
themselves during the contact time.
• The overall process normally involves several preliminary steps, not shown
here, to prepare the part for the silver plating.
• For many applications, an undercoating of copper is plated
first and then silver is plated over the copper.
• Silver plating is industrially important because silver is good
conductor, is resistant to corrosion and is generally considered
attractive.
Electrolysis and Stoichiometry
Current and Charge

Charge =Current X Time

Q=IXT
SI unit for power is the watt; 1watt =1 J/s
One kilowatt-hour = 3.6 x 10*6 J
1J = 1CV

Example Problem – No.4,5,6 and 7

 Batteries in Engineering Design
• One new type of battery (lithium ion battery)
• Successful product ranging from the iPhone to Tesla’s electrical cars.
• In 2013, Dreamliner was grounded, lithium ion batteries over heated and
caught fire in flight.
• More recently, Galaxy Note 7 and recall millions of phones after which
batteries caught fire.
• First,Dreamliner requires higher levels of electrical power than more
conventional aircraft.
• Second, increased fuel efficiency was a major goal in the Dreamliner design,
and so important to minimise weight .
• The compacting demands for high energy capacity and low weight to use
lithium ion batteries.
• Nickel metal hydride batteries are used in many hybrid cars.
• In this case semi permeable separator allow the flow of lithium ion between
the anode and cathode compartment.
• Anode is a form of graphite into the lithium atom have incorporated or
intercalated.
• Cathode is cobalt oxide.
• Dreamliner and Note 7 incident-the batteries can catch fire.
• Estimates suggest that about 1battery out 10000000 might be expected
to catch fire.
• Lithium ion battery are used in cell phone, laptops and other portable
devices.
• Important to recognise that danger of fire is one that can be minimised
with appropriate design.
• In both the Dreamliner and Note 7 cases, combination of design errors
and manufacturing defects caused unacceptably high failure rate.
Thank you so much for your attention