ELECTROCHEMISTRY

SUBMITTED TO:
Mr. DEEPAK AGGARWAL
H.O.D CHEMISTRY
SUMIT SINGH
CLASS: XII “SCIENCE”
 ACKNOWLEDGEMENT

First and foremost I thank my teacher Mr.

DEEPAK AGGARWAL who has assigned me this
project to bring out my creative capabilities.

I express my gratitude to my parents for being a

continuous source of encouragement for all their
financial aid.

My heartfelt gratitude to my class-mates and for

helping me to complete my work in time.
 Electrochemical Cells
Many oxidation-reduction reactions occur spontaneously, giving off energy. An example
involves the spontaneous reaction that occurs when zinc metal is placed in a solution of
copper ions as described by the net ionic equation shown below.

Cu+2 (aq) + Zn (s) -------> Cu(s) + Zn+2 (aq)

The zinc metal slowly "dissolves" as its oxidation produces zinc ions which enter into
solution. At the same time, the copper ions gain electrons and are converted into copper
atoms which coats the zinc metal or sediments to the bottom of the container. The
energy produced in this reaction is quickly dissipated as heat, but it can be made to do
useful work by a device called, an electrochemical cell. This is done in the following way.

An electrochemical cell is composed to two compartments or half-cells, each composed

of an electrode dipped in a solution of electrolyte. These half-cells are designed to
contain the oxidation half-reaction and reduction half-reaction separately as shown
below.

The half-cell, called

the anode, is the site at which
the oxidation of zinc occurs
as shown below.

Zn (s) ----------> Zn+2 (aq) +

2e-

During the oxidation of zinc,

the zinc electrode will slowly
dissolve to produce zinc ions
(Zn+2), which enter into the
solution containing
Zn (aq) and SO4-2 (aq)
+2
ions.

The half-cell, called the cathode, is the site at which reduction of copper occurs as
shown below.

Cu+2 (aq) + 2e- -------> Cu (s)

When the reduction of copper ions (Cu+2) occurs, copper atoms accumulate on the
surface of the solid copper electrode.

The reaction in each half-cell does not occur unless the two half cells are connected to
each other.
Recall that in order for oxidation to occur, there must be a corresponding reduction
reaction that is linked or "coupled" with it. Moreover, in an isolated oxidation or
reduction half-cell, an imbalance of electrical charge would occur, the anode would
become more positive as zinc cations are produced, and the cathode would become
more negative as copper cations are removed from solution. This problem can be solved
by using a "salt bridge" connecting the two cells as shown in the diagram below. A "salt
bridge" is a porous barrier which
prevents the spontaneous mixing of
the aqueous solutions in each
compartment, but allows the
migration of ions in both directions
to maintain electrical neutrality.
As the oxidation-reduction reaction
occurs, cations ( Zn ) from
+2
the anode
migrate via the salt bridge to the
cathode, while the anion, (SO4) ,
-2

migrates in the opposite direction to

maintain electrical neutrality.

The two half-cells are also connected

externally. In this arrangement, electrons provided by the oxidation reaction are forced
to travel via an external circuit to the site of the reduction reaction. The fact that the
reaction occurs spontaneously once these half cells are connected indicates that there is
a difference in potential energy. This difference in potential energy is called
an electomotive force (emf) and is measured in terms of volts. The zinc/copper cell has
an emf of about 1.1 volts under standard conditions.

Any electrical device can be "spliced" into the external circuit to utilize this potential
energy produced by the cell for useful work. Although the energy available from a single
cell is relatively small, electrochemical cells can be linked in series to boost their energy
output. A common and useful application of this characteristic is the"battery". An
example is the lead-acid battery used in automobiles. In the lead-acid battery, each cell
has a lead metal anode and lead (IV) oxide (lead dioxide) cathode both of which are
immersed in a solution of sulfuric acid. This single electrochemical cell produces about
2 volts. Linking 6 of these cells in series produces the 12-volt battery found in most cars
today. One disadvantage of these "wet cells" such as the lead-acid battery is that it is
very heavy and bulky. However, like many other "wet cells", the oxidation-reduction
reaction which occurs can be readily reversed via an external current such as that
provided by an automobile's alternator. This prolongs the lifetime and usefulness of
such devices as an energy source.

Standard Hydrogen Electrode (SHE)

The SHE is the universal reference for reporting relative half-cell potentials. It is a type
of gas electrode and was widely used in early studies as a reference electrode, and as an
indicator electrode for the determination
of pH values. The SHE could be used as either an anode or
cathode depending upon the nature of the half- cell it is
used with. The SHE consists of a platinum electrode
immersed in a solution with a hydrogen ion
concentration of 1.00M. The platinum electrode is made of
a small square of platinum foil which is platinized
(known as platinum black). Hydrogen gas, at a pressure of
1 atmosphere, is bubbled around the platinum electrode.
The platinum black serves as a large surface area for
the reaction to take place, and the stream of hydrogen
keeps the solution saturated at the electrode site with
respect to the gas. It is interesting to note that even
though the SHE is the universal reference standard, it
exists only as a theoretical electrode which scientists use as the definition of an
arbitrary reference electrode with a half-cell potential of 0.00 volts. (Because half-cell
potentials cannot be measured, this is the perfect electrode to allow scientists to
perform theoretical research calculations.) The reason this electrode cannot be
manufactured is due to the fact that no solution can be prepared that yields a hydrogen
ion activity of 1.00M.

hydrogen electrode is made by adding platinum black to platinum wire or a platinum

plate. It is immersed in the test solution and an electric charge is applied to the solution
and platinum black with hydrogen gas. The hydrogen-electrode method is a standard
among the various methods for measuring pH. The values derived using other methods
become trustworthy only when they match
those measured using hydrogen electrode
method. However, this method is not
appropriate for daily use because of the effort
and expense involved, with the inconvenience
of handling hydrogen gas and great influence
of highly oxidizing or reducing substances in
the test solution.

Fuel cell
A fuel cell is a device that generates electricity
by a chemical reaction. Every fuel cell has two electrodes, one positive and one negative,
called, respectively, the anode and cathode. The reactions that produce electricity take
place at the electrodes.

Every fuel cell also has an electrolyte, which carries electrically charged particles from
one electrode to the other, and a catalyst, which speeds the reactions at the electrodes.
Hydrogen is the basic fuel, but fuel cells also require oxygen. One great appeal of fuel
cells is that they generate electricity with very little pollution—much of the hydrogen
and oxygen used in generating electricity ultimately combine to form a harmless
byproduct, namely water.

One detail of terminology: a single fuel cell generates a tiny amount of direct current
(DC) electricity. In practice, many fuel cells are usually assembled into a stack. Cell or
stack, the principles are the same.

How do fuel cells work?

The purpose of a fuel cell is to produce an electrical current that can be directed outside
the cell to do work, such as powering an electric motor or illuminating a light bulb or a
city. Because of the way electricity behaves, this current returns to the fuel cell,
completing an electrical circuit. (To learn more about electricity and electric power,
visit “Throw The Switch” on the Smithsonian website Powering a Generation of
Change.) The chemical reactions that produce this current are the key to how a fuel cell
works.

There are several kinds of fuel cells, and each operates a bit differently. But in general
terms, hydrogen atoms enter a fuel cell at the anode where a chemical reaction strips
them of their electrons. The hydrogen atoms are now “ionized,” and carry a positive
electrical charge. The negatively charged electrons provide the current through wires to
do work. If alternating current (AC) is needed, the DC output of the fuel cell must be
routed through a conversion device called an inverter.

Oxygen enters the fuel cell at the cathode and, in some cell types (like the one
illustrated above), it there combines with electrons returning from the electrical circuit
and hydrogen ions that have traveled through the electrolyte from the anode. In other
cell types the oxygen picks up electrons and then travels through the electrolyte to the
anode, where it combines with hydrogen ions.

The electrolyte plays a key role. It must permit only the appropriate ions to pass
between the anode and cathode. If free electrons or other substances could travel
through the electrolyte, they would disrupt the chemical reaction.

Whether they combine at anode or cathode, together hydrogen and oxygen form water,
which drains from the cell. As long as a fuel cell is supplied with hydrogen and oxygen,
it will generate electricity.

Even better, since fuel cells create electricity chemically, rather than by combustion,
they are not subject to the thermodynamic laws that limit a conventional power plant
(see “Carnot Limit” in the glossary). Therefore, fuel cells are more efficient in extracting
energy from a fuel. Waste heat from some cells can also be harnessed, boosting system
efficiency still further.
 So why can’t I go out and buy a fuel cell?
The basic workings of a fuel cell may not be difficult to illustrate. But building
inexpensive, efficient, reliable fuel cells is a far more complicated business.

Scientists and inventors have designed many different types and sizes of fuel cells in the
search for greater efficiency, and the technical details of each kind vary. Many of the
choices facing fuel cell developers are constrained by the choice of electrolyte. The
design of electrodes, for example, and the materials used to make them depend on the
electrolyte. Today, the main electrolyte types are alkali, molten carbonate, phosphoric
acid, proton exchange membrane (PEM) and solid oxide. The first three are liquid
electrolytes; the last two are solids.

The type of fuel also depends on the electrolyte. Some cells need pure hydrogen, and
therefore demand extra equipment such as a “reformer” to purify the fuel. Other cells
can tolerate some impurities, but might need higher temperatures to run efficiently.
Liquid electrolytes circulate in some cells, which requires pumps. The type of
electrolyte also dictates a cell’s operating temperature–“molten” carbonate cells run
hot, just as the name implies.

Each type of fuel cell has advantages and drawbacks compared to the others, and none
is yet cheap and efficient enough to widely replace traditional ways of generating
power, such coal-fired, hydroelectric, or even nuclear power plants.

The following list describes the five main types of fuel cells. More detailed information
can be found in those specific areas of this site.

Different types of fuel cells.

Alkali fuel cells operate on compressed hydrogen and oxygen. They generally use a
solution of potassium hydroxide (chemically, KOH) in water as their electrolyte.
Efficiency is about 70 percent, and operating temperature is 150 to 200 degrees C,
(about 300 to 400 degrees F). Cell output ranges from 300 watts (W) to 5 kilowatts
(kW). Alkali cells were used in Apollo spacecraft to provide both electricity and
drinking water. They require pure hydrogen fuel, however, and their platinum electrode
catalysts are expensive. And like any container filled with liquid, they can leak.

Molten Carbonate fuel cells (MCFC) use high-temperature compounds of salt (like
sodium or magnesium) carbonates (chemically, CO3) as the electrolyte. Efficiency
ranges from 60 to 80 percent, and operating temperature is about 650 degrees C (1,200

degrees F). Units with output up to 2

Drawing of a molten carbonate cell
megawatts (MW) have been constructed, and
designs exist for units up to 100 MW. The high
temperature limits damage from carbon
monoxide "poisoning" of the cell and waste heat
can be recycled to make additional electricity.
Their nickel electrode-catalysts are inexpensive
compared to the platinum used in other cells.
But the high temperature also limits the
materials and safe uses of MCFCs—they would
probably be too hot for home use. Also,
carbonate ions from the electrolyte are used up
in the reactions, making it necessary to inject
carbon dioxide to compensate.

Phosphoric Acid fuel cells (PAFC) use phosphoric acid as the electrolyte. Efficiency
ranges from 40 to 80 percent, and operating temperature is between 150 to 200
degrees C (about 300 to 400 degrees F). Existing phosphoric acid cells have outputs up
to 200 kW, and 11 MW units have been tested. PAFCs tolerate a carbon monoxide
concentration of about 1.5 percent, which broadens the choice of fuels they can use. If
gasoline is used, the sulfur must be removed. Platinum electrode-catalysts are needed,
and internal parts must be able to withstand the corrosive acid.

.
Proton Exchange
Membrane (PEM) fuel cells work
with a polymer electrolyte in the
form of a thin, permeable sheet.
Efficiency is about 40 to 50 percent,
and operating temperature is about
80 degrees C (about 175 degrees
F). Cell outputs generally range
from 50 to 250 kW. The solid,
flexible electrolyte will not leak or
crack, and these cells operate
at a low enough
temperature to make them suitable
for homes and cars. But their
fuels must be purified, and a
platinum catalyst is used on both
sides of the membrane, raising
costs.

Solid Oxide fuel cells (SOFC) use a hard, ceramic compound of metal (like calcium or
zirconium) oxides (chemically, O2) as electrolyte. Efficiency is about 60 percent, and
operating temperatures are about 1,000 degrees C (about 1,800 degrees F). Cells output
is up to 100 kW. At such high temperatures a reformer is not required to extract
hydrogen from the fuel, and waste heat can be recycled to make additional electricity.
However, the high temperature limits applications of SOFC units and they tend to be
rather large. While solid electrolytes cannot leak, they can crack.

More detailed information about each fuel cell type, including histories and current
applications, can be found on their specific parts of this site. We have also provided a
glossary of technical terms–a link is provided at the top of each technology page.

Mercuric-Oxide Zinc Cell

The mercuric-oxide zinc cell (mercury cell) is a primary cell that was developed
during World War II. Two important assets of the mercury cell are its ability to produce
current for a long period of time and a long shelf life when compared to the dry cell
shown in figure 2-4.The mercury cell also has a very stable output voltage and is a
power source that can be made in a small physical size.

With the birth of the space program and the development of small transceivers and
miniaturized equipment, a power source of small size was needed. Such equipment
requires a small cell which is capable of delivering maximum electrical energy at a
constant discharge voltage. The mercury cell, which is one of the smallest cells, meets
these requirements.
Present mercury cells are manufactured in three basic types as shown in figure 2-5. The
wound-anode type, shown in figure 2-5 view A, has an anode composed of a corrugated
zinc strip with a paper absorbent. The zinc is mixed with mercury, and the paper is
soaked in the electrolyte which causes it to swell and press against the zinc and make
positive contact. This process ensures that the electrolyte makes contact with the
anode.

Figure 2-5. - Mercury cells.

In the pressed-powder cells, shown in figure 2-5 views B and C, the zinc powder for
the anode is mixed prior to being pressed into shape. The absorbent shown in the figure
is paper soaked in the electrolyte. The space between the inner and outer containers
provides passage for any gas generated by an improper chemical balance or impurities
present within the cell.

If the anode and cathode of a cell are connected together without a load, a SHORT
CIRCUIT condition exists. Short circuits (shorts) can be very dangerous. They cause
excessive heat, pressure, and current flow which may cause serious damage to the cell
or be a safety hazard to personnel.

WARNING
Do not short the mercury cell. Shorted mercury cells have exploded with considerable
force.

PRIMARY DRY CELL

The dry cell is the most popular type of primary cell. It is ideal for simple applications
where an inexpensive and noncritical source of electricity is all that is needed.

The dry cell is not actually dry. The electrolyte is not in a liquid state, but is a moist
paste. If it should become totally dry, it would no longer be able to transform chemical
energy to electrical energy.
 The construction of a common type of dry cell is shown in figure 2-4. These dry cells
are also referred to as Leclanche' cells. The internal parts of the cell are located in a
cylindrical zinc container. This zinc container serves as the negative electrode (cathode)
of the cell. The container is lined with a nonconducting material, such as blotting paper,
to separate the zinc from the paste. A carbon electrode is located in the center, and it
serves as the positive terminal (anode) of the cell. The paste is a mixture of several
substances such as
ammonium chloride,
powdered coke, ground
carbon, manganese dioxide,
zinc chloride, graphite, and
water.

Figure 2-4. - Cutaway view

of the general-purpose dry
cell.

This paste, which is

packed in the space between the anode and the blotting paper, also serves to hold the
anode rigid in the center of the cell. When the paste is packed in the cell, a small space is
left at the top for expansion of the electrolytic paste caused by the depolarization
action. The cell is then sealed with a cardboard or plastic seal.

Since the zinc container is the cathode, it must be protected with some insulating
material to be electrically isolated. Therefore, it is common practice for the
manufacturer to enclose the cells in cardboard and metal containers.

The dry cell (fig. 2-4) is basically the same as the simple voltaic cell (wet cell)
described earlier, as far as its internal chemical action is concerned. The action of the
water and the ammonium chloride in the paste, together with the zinc and carbon
electrodes, produces the voltage of the cell. Manganese dioxide is added to reduce
polarization when current flows and zinc chloride reduces local action when the cell is
not being used.

A cell that is not being used (sitting on the shelf) will gradually deteriorate because of
slow internal chemical changes (local action). This deterioration is usually very slow if
cells are properly stored. If unused cells are stored in a cool place, their shelf life will be
greatly preserved. Therefore, to minimize deterioration, they should be stored in
refrigerated spaces.

The blotting paper (paste-coated pulpboard separator) serves two purposes - (1) it
keeps the paste from making actual contact with the zinc container and (2) it permits
the electrolyte from the paste to filter through to the zinc slowly. The cell is sealed at the
top to keep air from entering and drying the electrolyte. Care should be taken to
prevent breaking this seal.
Nickel-Cadmium CellThe nickel-cadmium cell is a secondary cell, and the electrolyte is
potassium hydroxide.
Thenegative electrode is made of nickel
hydroxide, and the positive
electrode is made of
cadmiumhydroxide. The
nominal voltage of a nickel-
cadmium cell is 1.25 volts. The nickel-
cadmiumbattery has the
advantage of being a dry cell that is
a true storage battery with a
reversiblechemical reaction (i.e., it can
be recharged). The nickel-cadmium battery is a rugged, dependablebattery. It gives
dependable service under extreme conditions of temperature, shock, andvibration.
Due to its dependability, it is ideally suited for use in portable
communicationsequipment

Salt Bridge
The two compartments of a cell must be separated so they do not mix, but cannot be
completely separated with no way for ions to be transferred. Because of this, a salt
bridge is an important part of a concentration cell. It solves the major problem of
electrons beginning to pile up to much in the right beaker. This build up is due to
electrons moving from the left side, or left beaker, to the right side, or right
beaker. The salt bridge itself can be in a few different forms, such as a salt solution in
a U-tube or a porous barrier (direct contact). It evens the charge by moving ions to
the left side, or left beaker. In the written expression which shows what is occurring
in specific reactions, the salt bridge is represented by the double lines. An example of
this would be:

The double lines between the Zn2+ (1M) and the Cu2+ (1M) is the salt bridge. The
single lines do not represent bridges, they represent the different phase changes. If
there is a comma where you would expect to see a single line, this is not incorrect.
Instead it means that no phase changes occurred.

Standard Electrode Potentials

In an electrochemical cell, an electric potential is created between two dissimilar

metals. This potential is a measure of the energy per unit charge which is available from
the oxidation/reduction reactions to drive the reaction. It is customary to visualize the cell reaction
in terms of two half-reactions, an oxidation half-reaction and a reduction half-reaction.

Reduced species -> oxidized species + ne- Oxidation at anode

Oxidized species + ne- -> reduced species Reduction at cathode
The cell potential (often called the electromotive force or emf) has a contribution from
the anode which is a measure of its ability to lose electrons - it will be called its
"oxidation potential". The cathode has a contribution based on its ability to gain
electeons, its "reduction potential". The cell potential can then be written

Ecell = oxidation potential + reduction potential

If we could tabulate the oxidation and reduction potentials of all available electrodes,
then we could predict the cell potentials of voltaic cells created from any pair of
electrodes. Actually, tabulating one or the other is sufficient, since the oxidation
potential of a half-reaction is the negative of the reduction potential for the reverse of
that reaction. Two main hurdles must be overcome to establish such a tabulation

1. The electrode potential cannot be determined in isolation, but in a reaction with

some other electrode.
2. The electrode potential depends upon the concentrations of the substances, the
temperature, and the pressure in the case of a gas electrode.

In practice, the first of these hurdles is overcome by measuring the potentials with
respect to a standard hydrogen electrode. It is the nature of electric potential that
the zero of potential is arbitrary; it is the difference in potential which has practical
consequence. Tabulating all electrode potentials with respect to the same standard
electrode provides a practical working framework for a wide range of calculations and
predictions. The standard hydrogen electrode is assigned a potential of zero volts.

The second hurdle is overcome by choosing standard thermodynamic conditions for the measurement of the
potentials. The standard electrode potentials are customarily determined at solute concentrations of 1 Molar,
gas pressures of 1 atmosphere, and a standard temperature which is usually 25°C. The standard cell potential
is denoted by a degree sign as a superscript.

1. Measured against standard hydroden electrode.

2. Concentration 1 Molar

E °
Cell
3.
4.
Pressure 1 atmosphere
Temperature 25°C

Electrochemical
corrosion of iron
Corrosion often begins at a
location (1) where the metal
is under stress (at a bend or
weld) or is isolated from the
air (where two pieces of metal
are joined or under a
loosely-adhering paint film.)
The metal ions dissolve in the
 moisture film and the electrons migrate to another location (2) where they are taken up
by a depolarizer. Oxygen is the most common depolarizer; the resulting hydroxide ions
react with the Fe2+ to form the mixture of hydrous iron oxides known as rust.

CONTROL OF CORROSION
Since both the cathodic and anodic steps must take place for corrosion to occur,
prevention of either one will stop corrosion. The most obvious strategy is to stop both
processes by coating the object with a paint or other protective coating. Even if this is
done, there are likely to be places where the coating is broken or does not penetrate,
particularly if there are holes or screw threads.

A more sophisticated approach is to apply a slight negative charge to the metal, thus
making it more difficult for the reaction M → M2+ + 2 e– to take place.

Sacrificial coatings

One way of supplying this negative charge is to apply a coating of a more active metal.
Thus a very common way of protecting steel from corrosion is to coat it with a thin
layer of zinc; this process is known as galvanizing.The zinc coating, being less noble
than iron, tends to corrode selectively. Dissolution of this sacrificial coating leaves
behind electrons which concentrate in the iron, making it cathodic and thus inhibiting
its dissolution.

The effect of plating iron with a less active metal provides an interesting contrast. The
common tin-plated can (on the right) is a good example. As long as the tin coating
remains intact, all is well, but exposure of even a tiny part of the underlying iron to the
moist atmosphere initiates corrosion. The electrons released from the iron flow into the
tin, making the iron more anodic so now the tin is actively promoting corrosion of the
iron! You have probably observed how tin cans disintegrate very rapidly when left
outdoors.

Cathodic protection

A more sophisticated strategy is to maintain a continual negative electrical charge on a

metal, so that its dissolution as positive ions is inhibited. Since the entire surface is
forced into the cathodic condition, this method is known as cathodic protection. The
source of electrons can be an external direct current power supply (commonly used to protect oil pipelines
and other buried structures), or it can be the corrosion of another, more active metal such as a piece of zinc
or aluminum buried in the ground nearby, as is shown in the illustration of the buried propane storage tank
below.

HYDROGEN ECONOMY
It seems like every day there is a new announcement in the news about automobiles
powered by fuel cells. The promises are tantalizing, since fuel cells have the potential to
very quickly double theefficiency of cars while significantly reducing air pollution.
At the same time, there have been news
stories for decades about the problems
associated with petroleum.
Everything from oil spills to ozone
alerts to global warminggets blamed on our
dependence on fossil fuels.
These two forces are leading the world
toward what is broadly known as
the hydrogen economy. If the predictions
are true, over the next several decades we
will all begin to see an amazing shift away
from the fossil fuel economy we have today
toward a much cleaner hydrogen future.
Can society actually make this shift, or will the technological, economic and political
barriers keep us bound to petroleum and other fossil fuels for the next century and
beyond? In this article, you will learn about the benefits of a hydrogen economy, along
with its potential problems. We will also examine some of the technology that would
make the transition possible.