ELECTROCHEMISTRY

Lesson Objectives
Learner will be able to:
• Describe a conductor, insulator, electrolyte, non electrolyte with
examples.
• Describe electrolysis, an electrolytic cell and the reactions
occurring at the electrodes.
• Explain the electrolysis of molten solutions using inert electrodes
with the ionic equations.
• Explain the electrolysis of aqueous solutions using inert electrodes
with the ionic equations.
• Explain the electrolysis of concentrated and dilute aqueous
solutions using inert electrodes with the ionic equations.
• Explain the electrolysis of aqueous solutions using active
electrodes with the ionic equations.
• Describe electroplating with the ionic equations.
 Conductors-Insulators, Electrolyte-Non
electrolyte
• A conductor is a substance that is able to conduct
electricity (because of free flowing electrons) eg:
metals and graphite while an insulator is one that is
not able to conduct electricity eg: non-metals.
• An electrolyte is a substance that ionize completely
in solution and is able to conduct electricity in
molten or aqueous solution.
• Non electrolytes do not dissociate into ions in
solution and therefore, these solutions do not
conduct electricity. Eg: molten S, sugar solution
 Examples of Electrolytes and Non
Electrolytes
Electrolyte Non-Electrolyte

Sulphuric acid Distilled water

Molten lead bromide Ethanol

Sodium chloride solution Petrol

Hydrochloric acid Paraffin

Copper chloride solution Molten sulphur

Sodium hydroxide solution Sugar solution

 Conductivity in metals and electrolytes
In metals/solids- (i) Electrons flow
• (ii) Conductivity depends on property of element.
• (iii) takes place in solids and liquids
• (iv) No chemical change occurs
Electrical conductivity ( occurs only in ionic , not covalent
compounds)
• In molten/aqueous substances- (i) Ions flow
• (ii) Conductivity depends on property of ionic
compound.
• (iii) takes place in liquids and solutions (not solids)
• (iv) Chemical decomposition occurs
 Electrolysis
Electrolysis is the technique of chemical
decomposition/breakdown of an ionic
compound in molten or aqueous solution by
passing an electric current.
For example, if electricity is passed
through molten lead bromide, the lead
bromide is broken down to form lead and
bromine.
PbBr2  Pb2+ + 2Br-
 Electrolytic Cell
• Apparatus in which electrolysis is carried out is
electrolytic cell.
• An electrolytic cell consists of two electrodes and an
electrolyte.
• Rods of conducting substances that carry current into
and out of the solution are known as electrodes-
negative electrode is known as cathode while a
positive electrodes is known as anode .
• Positive ions(metal ions or H+) moving towards
cathode are known as cations while negative ions
(non metal ions) moving towards anode are known as
anions.
During electrolysis
• Positively charged ions move to the
negative electrode/ cathode during
electrolysis. They receive electrons and
are reduced.
• Negatively charged ions move to the positive
electrode/ anode during electrolysis. They lose
electrons and are oxidised. The substance that
is broken down is called the electrolyte.
 Ionic half equations

• A half-equation shows you what happens at one of

the electrodes during electrolysis and are balanced.
Electrons are shown as e-.
• When positive metal ions (cations) arrive at the negative
electrode (the cathode), they gain electrons to form neutral
metal atoms. This is called reduction. For example:
Pb2+ + 2e- → Pb
• When negative non-metal ions (anions) arrive at the positive
electrode (the anode), they lose electrons to form neutral
atoms or molecules. This is called oxidation. For example:
2Br- → Br2 + 2e-
 Electrolysis of molten solutions
Example:
Sodium chloride is melted by
supplying heat (above 801
°C). Two electrodes are
inserted it, and an electric
current is passed through
the molten salt, then
chemical reactions take
place at the electrodes. ...
Chlorine gas bubbles out
above the anode and
molten Na collect at the
cathode.
 Electrolysis of molten NaCl
• At cathode: Na+ +e- Na
• At anode: Cl-  Cl + e-
Cl + Cl  Cl2
When molten ionic compound is electrolysed, metal is
always formed at cathode and the non-metal is formed
at the anode.
During electrolysis of molten solutions, the ions present
move to opposite electrodes where they lose their
charge .
Given below are some more examples:
 Complete the following table
Molten electrolyte Decomposition Cathode reaction Anode reaction
products
ZnCl2
PbBr2
KI
CuBr2
NaCl
 Answers- Egs of Electrolysis in Molten
substances
Molten electrolyte Decomposition Cathode reaction Anode reaction
products
ZnCl2 Zinc and Chlorine Zn2+ + 2e-  Zn 2Cl-  Cl2 + 2e-
PbBr2 Lead and Bromine Pb2+ + 2e-  Pb 2Br-  Br2 + 2e-
KI Potassium and K+ + e -  K 2I-  I2 + 2e-
iodine
CuBr2 Copper and Cu2+ + 2e-  Cu 2Br-  Br2 + 2e-
Bromine
NaCl Sodium and Na+ + e-  Na 2Cl-  Cl2 + 2e-
Chlorine
 Electrolysis of ionic solutions using inert
electrodes
• Ionic solution has 4 ions-the water molecules
provide hydrogen ions (H+) and hydroxide ions
(OH-), in addition to the ions from the salt.
• At the cathode: Metal ions and hydrogen ions
are positively charged and discharge at the
cathode. Whether you get the metal or
hydrogen during electrolysis depends on the
position of the metal in the reactivity series:-
the more reactive the metal(than hydrogen), it
tends to stay as ions in solution. H+ ions will
accept electrons instead and hydrogen will
be produced at cathode leaving the metal
behind in solution. If metal is less reactive
eg: Cu, Cu2+ will accept e- readily and form
metal atoms and metal is discharged at
cathode leaving H+ ions in solution.
 At the positive electrode/anode

At the anode
If the negative ion from the ionic
Eg: the electrolysis of copper chloride
compound is simple like halogen(eg: solution produces copper at the
Cl-/ Br-) present in high concentration, negative electrode. However, the
then they give up electrons more readily electrolysis of sodium chloride
than OH- and that element is produced solution produces hydrogen.
with OH- remaining in solution.
If no halogen ions are present, the OH- ions
will give up electrons more easily than
any other non-metal anion while if the
negative ion is a complex ion (eg NO3-,
SO42-, CO32-), then they are not
discharged in preference to OH- ions and
oxygen is produced from the hydroxide
ion present instead.
 Complete the table
Electrolyte Gas given off at anode/ Gas given/metal Subst left on
with reactions deposit at cathode electrolysis
Copper sulphate
Sodium sulphate
Silver nitrate
Conc Sodium
chloride
Copper nitrate
Silver sulphate
Sodium nitrate
 Examples
Electrolyte
of electrolysis
Gas given off at anode
in solutions:
Gas given/metal Subst left on
deposit at cathode electrolysis
Copper sulphate Oxygen Copper Sulphuric acid
4OH- 2H2O+O2+4e- Cu2+ + 2e- Cu

Sodium sulphate Oxygen Hydrogen Sodium

4OH-  O2 +2H2O +4e- 2H₂O+2e-H2+2OH- sulphate

Silver nitrate Oxygen Silver Nitric acid

4OH- O2 + 2H2O + 4e- 4Ag+ + 4e-  4Ag
Conc Sodium Chlorine Hydrogen Sodium
chloride 2Cl-  Cl2 + 2e- 2H+ + 2e-  H2 hydroxide
Copper nitrate Oxygen Copper Nitric acid
4OH-  O2 + 2H2O+ 4e- Cu2+ + 2e-  Cu
Silver sulphate Oxygen Silver Sulphuric acid
4OH- O2 + 2H2O + 4e- 4Ag+ + 4e-  4Ag
Sodium nitrate Oxygen Hydrogen Sodium
4OH- O2 + 2H2O + 4e- 2H+ + 2e-  H2 nitrate
 Electrolysis of concentrated solutions of halide/acid and very dilute solution of
halides/acids

• If acid or halide solution is concentrated,

Cations pr are Na+ and H+ and since Na is more reactive, H+ accept
e-’s
2H+ + 2e-  H2
Anions pr are Cl- and OH-,
Cl- discharged easily than OH-
2Cl-  Cl2 + 2e-
Na+ and OH- remain behind in solution as NaOH
• If an acid or halide solution is dilute, (eg NaCl)/ dil acid like HCl)
then oxygen will be given off instead of the halogen. This is
because the halide ions are outnumbered by the hydroxide ions
from the water.
Electrolysis of acid solutions
 Electroplating
• Electroplating is the process of plating one metal onto another by
means of electric current, to prevent corrosion of a metal, make it
look more attractive etc.
• Electrolysis is used to electroplate objects (coat them with a thin
layer or metal). This is useful for coating a cheaper metal with a
more expensive one, such as copper or silver. Examples:
• Electroplating with silver
The object to be plated, such as a metal spoon, is connected to the
negative terminal of the power supply. A piece of silver is connected
to the positive terminal. The electrolyte is silver nitrate solution.
• Electroplating with copper
The object to be plated, such as a metal pan, is connected to the
negative terminal of the power supply. A piece of copper is
connected to the positive terminal. The electrolyte is copper sulfate
solution.
 Electroplating
Cathode: Object to be electroplated.
Anode: Metal used for electoplating-
Cu, Cr, Ag, Sn
Electrolyte: Salt of the metal that is
used for electroplating.
As the process proceeds, the metal
atoms lose electrons passing into
solution thus anode dissolves into
solution. The metal ions are in turn
discharged at cathode as the object is
plated and concentration of the
solution is the same.
 Electrolysis using active electrode- Purifying copper by
electrolysis

• Copper is purified by electrolysis. Electricity is passed

through solutions containing copper compounds, such
as copper(II) sulfate. The anode (positive electrode) is
made from impure copper and the cathode (negative
electrode) is made from pure copper. Anode:
Cu → Cu2+ + 2e- (oxidation)
Cathode: Pure copper forms on the cathode. Cu 2+ +
2e- → Cu (reduction)
Oxidation occurs at the anode because electrons are
lost & reduction at the cathode because electrons are
gained.
 Refining of copper
• A beaker with pure and impure copper rods
dipped into copper(II) sulfate solution
• During electrolysis, the anode loses mass
becoming thinner as copper dissolves, and the
cathode gains mass thickening as copper is
deposited on it.
Eg: Refining of Cu
• Blocks of impure copper are used as anode, thin
sheets of pure copper are cathode while
electrolyte is acidified CuSO4 solution.
• During refining, pure Cu is removed from impure
anodes and deposited on cathode while the
impurities fall to the bottom of the cell (anode
sludge).