Chapter 6.

2:
Electrochemistry

Lecturer: Uking Xiang

Contact: uking@alumni.usc.edu
WeChat: HelloUking

Contents:
• Section A: Conductivity in solids and liquids
• Section B: Electrolysis of electrolytes
• Section C: Hydrogen fuel cell
Section A: Conductivity in solids and liquids

a. Conductivity in solids – conductors and insulators

b. Conductivity in liquids – electrolytes and non-electrolytes
c. The electrolytic cell

a. Conductivity in solids – conductors and insulators

Testing a solid
material to see if
it conducts
electricity, by
whether it lights a
bulb.

For a solid to conduct, it must have a structure that contains ‘free’ electrons
that are able to flow through it.

There is a flow of electrons in the completed circuit. The battery acts as an

‘electron pump’ . Electrons are repelled (pushed) into the circuit from the
negative terminal of the battery. They are attracted to the positive terminal.
a. Conductivity in solids – conductors and insulators

Examples

Overhead power cables are made

from aluminium , which not only
conducts electricity well but has a low
density, preventing sagging.
Aluminium is also very resistant to
corrosion. The cables then strengthened
with a steel core.
b. Conductivity in liquids – electrolytes and non-electrolytes

The apparatus for

testing the conductivity
of liquids.

For liquid compounds or solutions, it must contains ‘free’ electrons or

ions that are able to flow through it.

b. Conductivity in liquids – electrolytes and non-electrolytes

b. Conductivity in liquids – electrolytes and non-electrolytes

Particles in ionic compounds are in fixed position in the solid state but can move
around when molten or in solution

b. Conductivity in liquids – electrolytes and non-electrolytes

The two distinct types of electrical conductivity are called

metallic and electrolytic conductivity. They differ from each
other in important ways.
c. The electrolytic cell

Components

Electrode is a rod of metal or graphite through which an electric current

flows into or out of an electrolyte
 Anode is the positive electrode of an electrolysis cell
• Anion is a negatively charged ion which is attracted to the anode
 Cathode is the negative electrode of an electrolysis cell
• Cation is a positively charged ion which is attracted to the cathode

Electrolyte is the ionic compound in molten or dissolved solution that

conducts the electricity

The direct current is supplied by a battery or power pack.

Electrons flow from the negative terminal of the battery around the
circuit and back to the positive terminal. In the electrolyte it is the
ions that move to carry the current.
 Section B: Electrolysis of electrolytes

a. Electrolysis of molten compounds

b. Electrolysis of solutions
c. Electrolysis Using metal electrodes

Decomposition brought about by electricity is called electrolysis.

a. Electrolysis of molten compounds

① Electrolysis of molten Zinc Chloride:

① Electrolysis of molten Zinc Chloride:

The cell decomposes the molten zinc chloride because the ions present
move to opposite electrodes where they lose their charge (they are
discharged).

at the anode

Cl⁻ → Cl + e⁻

Then two chlorine atoms bond together to make a chlorine molecule:

Cl + Cl → Cl₂

at the cathode

Zn²⁺ + 2e⁻ → Zn

② Electrolysis of molten Lead (II) Bromide:

 Electrolysis of molten Lead (II) Bromide:
 lead atoms are released at the negative electrode
 bromine molecules are released at the positive electrode.

First, the ions move.

Opposite charges attract.
So the positive lead ions (Pb²⁺) move
to the cathode (-).
The negative bromide ions (Br⁻) move
to the anode (+).
The moving ions carry the current.

Electrolysis of molten Lead (II) Bromide:

 lead atoms are released at the negative electrode
 bromine molecules are released at the positive electrode.

Ions gain electrons: reduction.

Electrolysis of molten Lead (II) Bromide:
 lead atoms are released at the negative electrode
 bromine molecules are released at the positive electrode.

Ions lose electrons: oxidation.

a. Electrolysis of molten compounds

a. Electrolysis of molten compounds—Application

③ Extraction of aluminium
from bauxite

Why used cryolite?

Why anodes replaced regularly?

a. Electrolysis of molten compounds—Application

③ Extraction of aluminium from bauxite
a. Electrolysis of molten compounds—Application
③ Extraction of aluminium from bauxite

at the anode

2O²⁻ → O₂ + 4e⁻

at the cathode

Al³⁺ + 3e⁻ → Al

The oxygen gas bubbles off, and reacts with the anode:
C (s) + O₂ ( g) → CO₂ ( g) (oxidation of carbon)
So the carbon blocks get eaten away, and need to be replaced.

The overall reaction The alumina is broken down, giving aluminium:

2Al₂O₃ (l) →4Al (l) + 3O₂ (g)

b. Electrolysis of solutions

at the cathode

 The more reactive a metal, the more it tends to stay as ions and not be
discharged. The H+ ions will accept electrons instead. Hydrogen
molecules will be formed, leaving the ions of the reactive metal, for
example Na+ ions, in solution.
 In contrast, the ions of less reactive metals, for example Cu2+ ions, will
accept electrons readily and form metal atoms. In this case, the metal
will be discharged, leaving the H+ ions in solution
 b. Electrolysis of solutions

at the anode

 If the ions of a halogen (Cl⁻, Br⁻ or I⁻) are present in a high enough
concentration, they will give up electrons more readily than OH−ions
will. Molecules of chlorine, bromine or iodine are formed. The OH−ions
remain in solution.
 If no halogen ions are present, the OH⁻ ions will give up electrons
more easily than any other non-metal anion. Sulfate and nitrate ions
are not discharged in preference to OH−ions. When OH−ions are
discharged, oxygen is formed.

b. Electrolysis of solutions

For a concentrated solution of sodium chloride

 b. Electrolysis of solutions

For a dilute solution of sodium chloride

b. Electrolysis of solutions—Application
The electrolysis of brine
b. Electrolysis of solutions—Application
The electrolysis of brine

Brine is a concentrated solution of sodium chloride, or common salt.

It can be obtained by pumping water into salt mines to dissolve the salt,
or by evaporating seawater.

at the cathode: Hydrogen is discharged in preference to sodium:

H⁺ + e⁻ → H₂

At the anode: Chlorine is discharged in preference to oxygen:

2Cl⁻ → Cl₂ + 2e⁻

The overall reaction The alumina is broken down, giving aluminium:

2NaCl (aq) + 2H₂O(l) → 2NaOH (aq) + Cl₂ (g) + H₂ (g)

b. Electrolysis of solutions—Application
b. Electrolysis of solutions—Application
Examples: electrolysis of concentrated CuCl₂ solution

Examples: electrolysis of solution

c. Electrolysis Using metal electrodes

c. Electrolysis Using metal electrodes

① The refining (purification) of copper by electrolysis
c. Electrolysis Using metal electrodes
① The refining (purification) of copper by electrolysis

at the cathode: gains mass as copper is deposited on it

Cu²⁺(aq) + 2e⁻ → Cu(s)

At the anode: loses mass as copper dissolves from it

Cu(s) → Cu²⁺(aq) + 2e⁻

So, overall, there is a transfer of copper from the anode to the cathode.
Th e colour of the copper(II) sulfate solution does not change because the
concentration of the Cu2+ ions remains the same.

c. Electrolysis Using metal electrodes

② Electroplating

Electroplating can be used to coat one metal with another.

c. Electrolysis Using metal electrodes
② Electroplating

at the cathode: The silver ions receive electrons, forming a coat of silver
on the jug

Ag⁺(aq) + e⁻ → Ag(s)

At the anode: The silver dissolves, forming silver ions in solution

Ag(s) → Ag⁺(aq) + e⁻

When the layer of silver is thick enough, the jug is removed.

c. Electrolysis Using metal electrodes

② Electroplating
 Why are objects electroplated?

 to protect the metal beneath from corroding

 to make the object look more attractive

 to increase the hardness of a surface and its resistance to scratching

 to save money by using a thin layer of a precious metal instead of

the pure expensive metal. This also helps people who are allergic to
nickel - a metal often used to make cheap jewellery.

Section C: Hydrogen fuel cell

Research has found a much more efficient way of changing chemical energy into
electrical energy by using a fuel cell. A hydrogen fuel cell can be used to power a car.
Section C: Hydrogen fuel cell

The energy produced on burning

one gram of various fuels, to
produce water and carbon
dioxide. Hydrogen produces
more energy per gram than any
other fuel.

Section C: Hydrogen fuel cell