Chemistry Handout 13 REF #: 013

Electrochemistry 1
An electric current is the flow of charged particles (electrons or ions)

Conductors and Insulators

A conductor of electricity is any substance which will allow the passage of an electric current through itself. Conduction
can either be

- Metallic Conduction
 Involves the movement of mobile
(free) electrons through metals
 The metal remains chemically
unchanged (only physical changes
occur)
 It does not involve the transfer of
matter
 Conductivity decreases with
increase in temperature- due to
the resistance offered to the
moving electrons by the vibration
of atoms.

Metal atoms have outer electrons which are not tied to any one atom. These electrons can move freely
within the structure of a metal when an electric current is applied.

- Electrolytic Conduction
 Involves the movement
of mobile (free ions) in a
molten substance or a
solution
 The molten substance or
the solution decomposes
(changes chemically and
physically)
 It involves the transfer of
matter in the form of
ions
 Conduction increases
with rise in temperature due to increase in the mobility of ions and to increase in the degree of
ionization of the electrolyte.

An insulator of electricity is any substance which will not allow the passage of an electric current through itself.
Electrons are localized and held in fixed position. They cannot move- so they cannot conduct electricity. There
are no such free electrons in covalent or ionic solids, so electrons can't flow through them - they are non-
conductors.

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Chemistry Handout 13 REF #: 013
Electrolyte- a molten substance or a solution that contains free ions and so allows electricity to pass through, e.g molten
salts, aqueous solutions of acids, alkalis and salts.

In the solid state of ionic substances, the ions are rigidly held together in the crystal lattice by strong electrostatic forces
and therefore cannot move around. This is why ionic solids cannot conduct electricity. In molten state or in a solution,
they are free to move around.

Non- Electrolyte- A molten substance or a solution that does not allow electricity to pass through because it does not
contain any free ions. E.g organic solvents, aqueous solutions of organic substances such as glucose, molten covalent
substances such as wax.

Strong and Weak Electrolytes

- Strong electrolytes are substances that are fully ionized and as such contain a large number of ions. E.g strong
acids, strong alkalis, solution of salts, molten salts.

- Weak electrolytes are substances that are partially ionized and as such contains a fewer number of ions. E.g
weak acids, weak alkalis, pure water.

Note: Pure water is an extremely weak electrolyte. Approximately one molecule in every 560 000 000 molecules is
ionized:

Electrolysis is defined as the chemical change that

occurs when an electric current is passes through an
electrolyte.

Electrolysis is the passage of an electric current

through an electrolyte causing it to decompose.

To understand electrolysis, you need to know

what an ionic substance is.

Ionic substances form when a metal reacts with

a non-metal. They contain charged particles
called ions. For example, sodium chloride forms
when sodium reacts with chlorine. It contains
positively charged sodium ions and negatively
charged chloride ions. Ionic substances can be
broken down by electricity.

Electrode- an electrode is a conductor through which electricity enters or leaves an object or substance. Electrolysis
involves the use of electrodes connected to a battery. The electrodes carry current into and out of the electrolyte.
Electrodes are usually made of inert (unreactive) materials e.g graphite (carbon), platinum.

Anode- the positive electrode connected to the positive terminal of the battery.

Cathode- the negative electrode connected to the negative terminal of the battery.

Anion- An atom which has gained electrons and has acquired a net negative charge or extra negative charge

Cation- An atom which has lost electrons and has acquired a net positive charge or less negative charge.

The Process of Electrolysis

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Chemistry Handout 13 REF #: 013
The key process of electrolysis is the interchange of atoms and ions by the removal or addition of electrons to the
external circuit. The required products of electrolysis are in a different physical from the electrolyte (solid and gas) and
are deposited at the electrodes which can then be removed by some physical process.

Each electrode attracts ions that are of the opposite charge.

1. Anions (-) are attracted to the anode (+).

These anions lose electrons to form neural
atoms. The formation of uncharged atoms
from ions is called discharging.
An- - ne-  A
Oxidation therefore occurs at the anode.
2. The battery is an ‘electron pump’, which
sucks the electrons out of the solution at
the anode and pushes them to the
cathode.
3. Electrons lost at the anode are sucked
along to the positive terminal of the
battery and pushed out of the negative
terminal the cathode.
4. Cations (+) are attracted to the cathode (-)
where they gain electrons lost from the
anode to form neutral atoms i.e they are
discharged.
Cn+ + ne-  C
Reduction therefore occurs at the
cathode.
5. As the ions move they carry the electric
charge through the electrolyte and a current flows around the circuit. This means that electrolysis is taking place
and an electrochemical reaction is happening.

Ions Present in the Electrolyte

Molten Electrolytes

Molten electrolytes contain only two kinds of ion. Both are discharged during electrolysis.

Aqueous Solutions

An aqueous solution usually contains at least two different cations and two different anions, owing to the presence of H +
and OH- ions from the water. Only one type of ion of each charge is usually discharged at each electrode.

The three factors which affects which ions are discharged:

Cation Anion 1. Position of the ion in the electrochemical series.

K+ SO42-
Ca2+ NO3- The electrochemical series is the arrangement of chemical elements based on
Na+ Cl- their standard electrode potential. A hydrogen electrode is taken as having
Mg2+ Br- zero electrode potential. Elements that have a greater tendency than hydrogen
to lose electrons to their solution are taken as electropositive; those that gain
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electronegative.
Chemistry Handout 13 REF #: 013
3+ -
Al I
Zn2+ OH-
Fe2+
Pb2+
H+
Cu2+
Ag+

2. Relative concentration of the ions

The greater the concentration of an ion, the more likely it is to be discharged. Irrespective of the position of the
ions in the electrochemical series, there is a tendency to promote the discharge of the most concentrated ion
present. For example, in concentrated sodium chloride solution (i.e. brine), the two anions present are the chlorine
ion and the hydroxyl ion. Although the hydroxyl ion is more easily oxidized than the chlorine ion, it is the chlorine
ion which will be discharged because its concentration is much greater than that of the hydroxyl.

3. Nature of the electrode

Usually, inert electrodes such as graphite or platinum are used for electrolysis. These electrodes do not interfere
with the reactions occurring at the surface of the electrode, they simply act as a point of connection between the
electrical circuit and the solution.
An electrode which is not inert can take part in a reaction. If an active electrode is used, then the reaction occurring
is the one that requires the least energy. Example: if metal electrodes are used in metal ion solutions they can get
involved in the reactions by dissolving as ions, leaving their electrons behind (this can only happen when the metal
takes the place of the anode, the positive electrode) - this is called electrode participation.

Applications of Electrolysis
1. Extraction of Reactive metals- Reactive metals are the metals that occupy the top positions in the
electrochemical series. Metals that are higher than zinc in the electrochemical series are extracted using
electrolysis. These very reactive metals cannot be extracted by other metals such as reduction with carbon. The
reactive metals are obtained by electrolyzing a molten ionic compound of metal.

2. Purification of metals (Electrorefining)- Most metals need to be purified as the presence of impurities affects the
properties of the metal, for example they can make impure iron brittle. The amount of different impurities
which may be present in the final sample of the metal depends on what the metal is used for. Iron, for example,
is rarely used in a pure form and impurities such as small amounts of carbon are important in steel, the main use
of iron. Copper is a valuable metal which is widely used, particularly as an electrical conductor, unfortunately
even small amounts of impurity can reduce its electrical conductivity considerably. To purify the metal an
electrolytic process is used, with a sheet of pure copper as the negative cathode, and the impure copper as the
positive anode. Copper dissolves from the anode to form copper ions, which are attracted to the cathode where
they are deposited as the pure metal. Any impurities fall to the bottom of the cell forming a 'sludge', which often
contains small amounts of silver and gold.

3. Electroplating- Electroplating is used to coat one metal with another metal by using electrolysis. Electroplating is
usually done to improve the appearance of the metal or prevent the corrosion of the metal. The cathode is the
object to be plated, while anode is the desired metal to coat the object. The electrolyte solution must contain
ions of the same metal for plating. During electrolysis, the anode will dissolve into the solution. The ions

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Chemistry Handout 13 REF #: 013
produced will migrate to the cathode where they are discharged and deposited as a layer on the cathode. It is
important to ensure that the cathode is electrically conductive. (If not, the electrolysis does not work.)

4. Anodizing- Anodizing is the method of producing a coating on objects, such as window frames and saucepans to
make them resistant to corrosion. When exposed to the air, aluminum combines with oxygen to form aluminum
oxide. The oxide forms an even coat and seals the surface, thus protecting the metal from further corrosion.
Anodizing is used to make the protective layer thicker and tougher.

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