Electrochemistry

Electrochemistry is the study and application of the fundamental principles of

electrochemical reactions. Electrochemical processes include electrolysis,
electroplating, and voltage cells. Electrochemistry principles include understanding
the role of anode and cathode, the movement of electrons in an external circuit, and
the migration of ions in an electrolyte.

Electrochemical cells
Devices that convert chemical energy into electrical energy or vice versa are called
electrochemical cells.
Therefore, there are two types of electrochemical cells:
(1) Electrolytic Cells
(2) Galvanic Cells

 A physical or chemical change that occurs by itself is called a spontaneous

process. Spontaneous processes do not require a source of energy to make
them happen.

 For instance, water flows from a higher level to a lower level. Iron placed in
moist air, rusts. The flow of electrons through a conductor can be obtained
from a spontaneous oxidation-reduction reaction. This is the basis for how
batteries work.

 A physical or chemical change that requires a source of energy to make it

happen is called a non-spontaneous process.

 For example, water can be made to flow from a lower level to a higher level
by using a pump.

Nature of Electrochemical Process

Electrochemical processes are oxidation- reduction reactions in which chemical
energy released by a spontaneous reaction is converted to electricity or in which
electrical energy is used to drive a non-spontaneous reaction. Whether an
electrochemical process releases or requires energy, it always involves the transfer of
electrons from one substance to another. This means that this process always involves
an oxidation-reduction or a redox reaction.

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Electrolyte and Non Electrolyte
 When an ionic compound is dissolved in water, it splits up into its positive
and negative ions, these ions are capable of conducting electricity. Such
compounds are referred to as electrolytes. Substances that can conduct
electricity when they are in a molten state or aqueous solution and undergo
chemical changes.
 Examples of electrolytes are NaCl, KCI, HCI, NaOH, etc.

 A substance that cannot conduct electricity when dissolved in water or in

the molten state is called a non-electrolyte.
 Examples of non-electrolytes are urea, glucose, sucrose, benzene etc.

Electrolytic Cells
An electrochemical cell in which electrical energy is used to drive a chemical reaction
is called an electrolytic cell.
An electrolytic cell consists of

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(a) A vessel containing an electrolyte (MX)
(b) Two inert electrodes
(c) A battery

Electrons move from anode to cathode in the outer circuit, in the solution the cations
move towards the cathode and anions towards anode. At the anode, anions oxidize by
losing electrons. At the cathode, cations reduce by gaining electrons. This means
oxidation occurs at the anode and reduction at the cathode. The electrons released by
anions at the anode move in the external circuit towards the cathode. This means the
movement of ions in the electrolyte and the transfer of electrons occur at electrodes in
the external circuit.
At Anode
X- →X +1e-
At cathode
M+ +le- → M

Electrolysis

Electrolysis is the chemical process in which an electric current is passed through an

electrolyte, either in its molten state or as an aqueous solution, causing a non-
spontaneous redox reaction to occur. This process involves the movement of ions
towards oppositely charged electrodes, where oxidation occurs at the anode and
reduction occurs at the cathode. This process leads to the decomposition of the
electrolyte or its components into simpler substances or elements.

Electrolysis of molten electrolyte

Electrolysis of Molten Sodium chloride

On a large scale, sodium metal is produced by the electrolysis of fused sodium
chloride. The electrolytic cell used in the process is called a Down's Cell. Down's Cell
uses an iron cathode and carbon anode. During the electrolysis, the sodium ions are
reduced at the cathode to liquid sodium metal. At the anode, the chloride ions are
oxidized to chlorine gas.
At anode
2Cl- →Cl2 + 2e-
At cathode
2Na+ +2e- →2Na

(ii) Electrolysis of molten lead(II) chloride using platinum or graphite electrodes

On a large scale, lead metal is produced by the electrolysis of molten or fused lead(II)
chloride. An electrolytic cell is used for this purpose. Molten lead chloride is placed in
the electrolytic tank and platinum, or graphite electrodes are dipped in it. The
electrolysis is conducted above 327°C, which is the melting point of lead chloride.
At anode:
2Cl- → Cl2 + 2e-
At cathode:
Pb2+ +2e- →Pb

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(ii) Electrolysis of molten lead(II) chloride using platinum or graphite electrodes
On a large scale, lead metal is produced by the electrolysis of molten or fused lead(II)
chloride. An electrolytic cell is used for this purpose. Molten lead chloride is placed in
the electrolytic tank and platinum, or graphite electrodes are dipped in it. The
electrolysis is conducted above 327°C, which is the melting point of lead chloride.
Molten lead chloride contains free lead ions and chloride ions. During electrolysis,
chloride ions move towards the anode and lead ions towards the cathode. At the
electrodes following reactions occur.
Molten lead is collected at the bottom of the cathode and chlorine gas at the anode.

Electrolysis of concentrated aqueous solution

Electrolysis of a concentrated aqueous solution of sodium chloride called brine is used
for the industrial production of sodium hydroxide. Electrolysis is carried out by using
inert electrodes such as platinum, or carbon (graphite).The brine contains sodium ions
and chloride ions from NaCl and hydrogen ions and hydroxide ions from
water.

During electrolysis, chloride ions move towards the anode. At anode chloride ions are
oxidized to produce chlorine gas. Sodium ions move towards the net Electrode
cathode. However, sodium ions are not reduced to sodium metals in this process.
Instead, hydrogen ions from water are discharged to produce hydrogen gas. More and
more water molecules keep ionizing to replace H" ions as soon as they are consumed.
The electrolyte in the solution becomes sodium hydroxide (NaOH). Following
reactions occur in the electrolytic cell.
The solution contains Na' and OH ions. Evaporation of water from this solution
produces pure solid sodium hydroxide.
At anode:
2Cl-→ Cl2 +2e-
At Cathode:
2H+ +2e- →H2

Electrolysis of dilute aqueous solution

Electrolysis of dilute aqueous Sodium chloride using platinum electrodes

Unlike electrolysis of concentrated aqueous sodium chloride, chloride ions are not
oxidized at the anode. Instead, hydroxide ions are oxidized and oxygen gas is
produced at the anode. Reaction at the cathode remains the same. And hydrogen is
produced at the cathode. The following reactions take place during electrolysis.
At Cathode:
4H+ +4e- →2H2
At anode:
4OH- → 2H2O + 4e- + O2

b. Electrolysis of dilute sulphuric acid using platinum electrodes

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In an aqueous solution, sulphuric acid ionizes to form hydrogen ions and sulphate ions.
Auto ionization of water gives hydrogen ions and hydroxide ions.
H2SO4 → 2H+ +SO 42-
H +
2O →2H + OH
-

During electrolysis, hydrogen ions move towards the cathode and are reduced to form
hydrogen. Whereas hydroxyl ions and sulphate ions move towards the anode. At the
anode, hydroxyl ions are oxidized and sulphate ions remain unchanged.
At cathode:
4H+ +4e-→2H2
At anode:
4OH- →2H2O+4e-+ O2

Therefore, in the electrolysis of dilute aqueous H,SO, using a platinum electrode,

hydrogen gas is produced at the cathode and oxygen gas at the anode.

Electrolysis of copper(II) sulphate using platinum electrodes

The aqueous solution of copper sulphate contains copper ions and sulphate ions from
copper(II) sulphate and hydrogen ions and hydroxide ions from water. During
electrolysis copper ions and hydrogen ions are attracted towards the cathode. At the
cathode, only copper ions are reduced and hydrogen ions remain unchanged. The
sulphate ions and hydroxide ions are attracted towards the anode. At the anode, only
hydroxide ions are oxidized and sulphate ions remain unchanged.
At cathode:
2Cu2+ +4e- → 2Cu
At anode
4OH- →2H2O+O2 +4e-

Therefore, in the electrolysis of aqueous copper(II)sulphate using a platinum electrode,

copper metal is produced at the cathode and oxygen gas at the anode. The blue colour
of the copper sulphate solution gradually fades away as the reaction goes on.

d. Electrolysis of copper(II) sulphate using copper electrodes

If you use copper electrodes rather than platinum, the cathode reaction remains the
same but the anode reaction differs. At anode, copper atoms break away from the
electrode forming Cu ions giving up electrons to the anode. These electrons are
moved towards the cathode by the power source. The following reactions occur
during electrolysis.
At Cathode:
Cu2+ +2e- →Cu
At anode:
Cu→ Cu2+ +2e-

During electrolysis copper anode is consumed gradually and the copper cathode gains
mass due to the deposition of pure copper on it.

The copper metal obtained from its ores is usually impure. It contains impurities such
as zinc, iron, silver and gold. These impurities are removed by the process deposit of
electrolysis. In this process, impure copper bars act as anode and pure copper bars as
cathode. CuSO4, a solution containing little sulphuric acid is used as the electrolyte.

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On passing electricity, copper anode dissolves forming Cu ions. Cations move
towards the cathode at which only Cu ions are reduced. Thus pure copper deposits
at the cathode. The less electropositive metals, silver and gold fall to the bottom of
the cell. Copper obtained in this process is 99.5% pure.

Electroplating (deposition using the same electrode)

The electrolytic process used to deposit one metal on another metal is called
electroplating. An object can be electroplated by making it cathode in an electrolytic
tank containing ions of the plating metal. The plating metal is made anode. On
passing electricity through the electrolytic tanks, a thin layer of anode metal is
deposited on the surface of the object.

Applications of Electroplating
Steel objects are often protected from corrosion by electroplating with zinc, tin and
chromium.

Zinc Plating
Zinc plating on steel is done by using zinc metal as anode. A solution of potassium
zinc cyanide K2[Zn(CN)4] containing little sodium cyanide is used as an electrolyte.
The steel object is made of cathode. During the electrolysis zinc at the anode enters
the solution as Zn12 ions, which are deposited at the cathode. The electrolyte ionizes
as follows.
K2[Zn(CN)4]⇌2K+ + [Zn(CN)4]2-
[Zn(CN)4]2-⇌ Zn2+ +4CN-
Sodium cyanide prevents the hydrolysis of electrolytes.
Awareness against pollution
Cyanide ions are extremely toxic. Therefore, a solution containing cyanide ions must
not be dropped into rivers and streams. This is responsible for killing fish and other
animals.

Tin Plating
Food cans are generally tin-plated. Tin plating on steel is done by using tin as an
anode and a solution of stannous sulphate, (Sn50,) as electrolyte. A few drops of dil.
H,SO, added to the electrolyte to prevent its hydrolysis. The electrolyte ionizes as

SnSO4⇌Sn+2 +2e-
follows.

At anode:
Sn→Sn2+ +2e-
At cathode
Sn+2 +2e-→ Sn

Electrolysis of halide compound

During the electrolysis of a halide compound (a compound containing halogen ions
like chloride, bromide, or iodide), the products depend on whether the solution is
dilute or concentrated. Here's a simple explanation:
1. Electrolysis of Dilute Halide Solution

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At the Anode: Oxygen gas is usually produced because water breaks down into
oxygen and hydrogen ions. This happens because the water molecules compete the
halide ions for discharge.
At the Cathode: Hydrogen gas is produced as water molecules are reduced to form
hydrogen gas and hydroxide ions.

Electrolysis of Concentrated Halide Solution

At the Anode: The halogen (chlorine, bromine, or iodine) is produced because there
are many halide ions, so they are discharged instead of water.
At the Cathode: Hydrogen gas is still produced because water is reduced.

Galvanic Cells (Daniel Cells)

The cell which involves a spontaneous redox reaction to generate electricity is called
a galvanic or voltaic cell.
Construction

Each compartment of the cell is called a half-cell. Thus a Daniel cell consists of two
half-cells joined in series. When the circuit is complete, electrons begin to flow from
the Zn rod through the external wires to the Cu rod. Thus Zn half-cell acts as an
anode and the Cu half- cell as a cathode. Note that a half cell consists of a metal rod
dipped in the solution of its salt.

Reactions in a Daniel Cell

Reduction half reduction occurs at the cathode compartment. Such oxidation and
reduction reactions are called half-cell reactions.
At Anode (Oxidation half reaction):

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 Zn→Zn+2 +2e-
At Cathode (Reduction half-reaction):
Cu+2 +2e- →Cu
Electrochemical Series
The tendency of a metal to become oxidized or reduced, when placed in its salt
solution is called electrode potential (E°).

 It is measured in volts.
 The electrode potential of an electrode is determined experimentally by
using a standard hydrogen electrode.
 The International Union of Pure and Applied Chemistry (IUPAC) has
recommended the representation of electrode potential as reduction
potentials.

A table showing the arrangement of metals based on increasing reduction potentials

is called an electrochemical series.

Electrochemical series helps us predict which substances will form at the electrodes
during electrolysis.
At the Cathode (Negative Electrode):
At the cathode positive ions (cations) gain electrons (reduction happens). The ion
lower in the electrochemical series (less reactive) is more likely to get reduced.
Example: If the solution contains sodium ions (Na) and hydrogen ions (H"), hydrogen
gas (H1) forms because hydrogen is lower in the series than sodium.

At the Anode (Positive Electrode):

At the anode negative ions (anions) lose electrons (oxidation happens). Halide ions
(Cl, Br, I) are discharged before hydroxide (OH) unless halides are absent. For
example: In a concentrated solution of sodium chloride, chloride ions (CI) are
discharged, producing chlorine gas (Cl,) because chlorine is lower in the series than
water.
However in the electrolysis of dilute aqueous NaCl, OH ions are discharged instead
of Cl ions, even though Cl- ions are lower in the electrochemical series This is due to
the following reasons.

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 Battery-A Source of Electrical Energy
A battery is a galvanic cell, or a group of galvanic cells joined in series. It generates
electric current by a redox reaction.

Working
When connected in a circuit its anode is oxidised by releasing electrons. These
electrons through the external circuit begin to flow towards the cathode. At the
cathode, these electrons reduce the oxidizing agent present in the electrolyte.
Examples of batteries are dry cells, storage cells, mercury batteries etc.

A Fuel Cell
A fuel cell is a special type of galvanic cell which is based upon the reaction between
oxygen and a gaseous fuel hydrogen. When hydrogen burns in air, an exothermic
reaction occurs and a lot of chemical energy is released in the form of heat and
light.

In this reaction, hydrogen is oxidized to water.

2H2 + O2 → 2H2O + Heat

The energy released from the reaction of hydrogen with oxygen to form water is
converted to electrical energy.
Construction

Anode reaction
2H2 + 4OH- → 4H2O +4e-
Cathode reaction
O2 +2H2O +4e-→4OH-
Net reaction
2H2+ O2→2H2O

A hydrogen-oxygen cell delivers 0.9 V.

The fuel cell operates at high temperatures so the water formed evaporates and may
be condensed.

Uses:
The fuel cells of this kind have been used by the American space program. The water
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condensed in spacecraft is consumed by the astronauts.

Advantages and disadvantages of fuel cells

 Hydrogen-oxygen fuel cells are highly efficient since they convert
fuel directly into electricity with very little waste.
 Fuel cells are a source of clean energy, as they do not produce
harmful pollutants. They emit water vapor only.
 Moreover, fuel cells are highly reliable, as they have no moving parts.
They also have a long life span with little maintenance.

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  Hydrogen oxygen used in fuel cells is obtained from renewable energy sources.
 Unlike fuel cells, gasoline-powered combustion engines in vehicles emit
pollutants, including carbon dioxide, oxides of nitrogen and sulphur, which
cause pollution and create smog. These pollutants cause respiratory
problems and other health issues.
 Gasoline is obtained from non-renewable sources of energy.

Fuel cells have a few disadvantages

 Hydrogen is highly inflammable and explosive in nature.
 It requires careful handling for storage and use. So, it cannot be transported
easily from one place to another.
 Hydrogen used in fuel cells is produced by electrolysis of water which is
very expensive.

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