Chapter 28

• We have seen that spontaneous redox reactions can be

used as a source of electrical energy.
• We can cause redox reactions to occur by the passage
of electrical energy from a power supply through a
conducting liquid.
• This process is called electrolysis.
• Electrical energy is converted into chemical energy.
• The reactions that occur in electrolytic cells are
essentially the opposite to those occurring in galvanic
cells.
• Reactions in electrolytic cells would not normally
happen without the application of electrical energy,
and so they are called non-spontaneous reactions.
• Chemicals formed by electrolysis are often difficult to
obtain by other means.
• Plating a thin film of metal on surfaces of other metals
to improve the appearance or prevent corrosion.
• Extraction of reactive metals such as sodium and
aluminium from their ores.
• Industrial production of sodium hydroxide, copper,
chlorine and hydrogen
• Recharging of car batteries and other rechargeable
cells, such as lithium batteries
• Increasing the thickness of the surface oxide layer on
aluminium metal to improve its resistance to
corrosion.
 We tend to take tin cans for granted.
 They are not really tin cans, but are mainly composed
of steel with a thin surface coating of tin only a fraction
of a millimetre thick that has been applied by
electrolysis.
 Tin corrodes very slowly and prevents contact between
the iron, moisture and air.
 It therefore prevents rusting.
• The deposition of a layer of metal on the surface of another
metal by electrolysis is called electroplating.
• It is performed in an electrolytic cell such as the simplified
one used for tin plating as shown.
• The object to be plated is connected by a wire to the
negative terminal of a power supply.
• This is the negative electrode of the cell.
• It is immersed in a solution, such as tin nitrate solution,
which contains ions of the metal that is to form the plating.
• This is the electrolyte
• An electrode of tin metal is connected to the positive
terminal of the power supply.
 When the cell is in operation the power supply acts as
an ‘electron pump’ pushing electrons onto the negative
electrode and removing electrons from the positive
electrode.
 At the negative electrode:
 The negative terminal of the power supply pushes
electrons along the wire to the electrode. Tin ions are
attracted to the electrode, accept electrons and are
converted to tin metal:
Sn2+(aq) + 2e- → Sn(s)
 A coating of tin forms on the object. Since reduction of
the tin ions has occurred, the negative electrode is
acting as a cathode.
• At the positive electrode:
– The positive terminal of the power supply withdraws
electrons from the tin electrode. A reaction that released
electrons must occur.
– Tin metal slowly dissolves as Sn2+ ions are formed:
Sn(s) → Sn2+(aq) + 2e
– This reaction replaces the Sn2+ ions in solution that were
consumed by the reaction at the negative electrode.
– Since an oxidation reaction has occurred the positive
electrode is the cathode.
• The excess of positive charge caused by the production
of Sn2+ ions at the anode will be balanced by
movement of NO3- ions in the electrolyte to that
region and by movement of Sn2+ ions away from it.
• At the cathode, loss of positive charge causes cations
to migrate towards it and anions away from it.
• It is still cations towards the cathode and anions away
from it.
 Iron is widely used because it is cheap and strong.
Electroplating with iron improves their resistance to
corrosion.
 Electroplating jewellery makes an object more
attractive.
 Chromium is used for decoration, non-tarnishing and
hard-wearing.
 Page 448
 Question 1 and 2
• When electroplating an object we need to know:
– How can I determine how much metal is being plated?
– How long should I leave the object being plated in the
electroplating cell?
– What size current should I use
• We can determine the electric charge needed to be
used by using this law.
 Electric charge, is given the symbol Q and is measured
in coulomb.
 The relationship is:
charge(coulombs) = current(amps) x time(sec)
Q=Ixt
 Look at the table on page 449 for the relationship
between charge and mass
 We can link this to mass as the mass of metal
produced at the cathode is directly proportional
to the quantity of electricity passed through the
cell.
 This relationship is known as Faraday’s first law of
electrolysis.
 It may be written as:
mαQ
 In order to deposit one mole of silver from a solution of
Ag+ ions, just one more of electrons is required:
Ag+(aq) + e- → Ag(s)
 The charge on one mole of electrons is 96 500C
 The charge on one mole of electrons is known as a
faraday, and given the symbol F.
1 Faraday = 96 500 coulomb mol-1.
 The charge on a given number of moles of electrons,
n(e-), may be calculated by:
Q = n(e-) x F
 In order to produce one mole of a metal, one, two,
three, or another whole number of moles of
electrons must be consumed.
 This is Faraday’s second law of electrolysis.
• 28.3a
• A silver-plating cell operates with a steady current of
30.0 A for 20.0 minutes. What mass of silver is plated
on the object at the cathode?
• 28.3b
• How long would it take to deposit 50.0 g of copper at
the cathode of the copper-plating cell operating at a
current of 8.00 A?
 Page 451
 Question 3 - 6
 Knowing that oxidation occurs at the anode and
reduction occurs at the cathode it is possible to predict
the electrode reactions in a particular electrolytic cell.
 Usually there are several chemicals present at each
electrode and you must decide which of the possible
reactions have the greatest tendency to occur.
 The highest reaction in the electrochemical series that
can occur in the forward direction is likely to occur at
the cathode.
 That is the strongest oxidant will usually react at the
cathode.
 The lowest reaction in the electrochemical series that
can occur in reverse is likely to occur at the anode.
 That is the strongest reductant will usually react at the
anode.
 It is the opposite to the Galvanic Cell
 Predict the products of electrolysis of 1 M nickel
sulfate solution using copper electrodes
 Page 452
 Question 7
 To be commercially viable, electrolysis processes must:
 Be located in places with access to cheap, abundant and reliable
electrical power.
 Use electrolytes that are cheap and readily available
 Where possible use electrodes made from inexpensive materials
such as carbon or iron
 Be sited in locations that allow relatively inexpensive transport of
materials and products
 Operate continuously – it should not be necessary to stop the cells
in order to add electrolyte or remove products
 Involve low electrolyte temperatures to reduce heating costs and
minimise wear on equipment
 Consider the environmental impact of the materials used in the
construction and operation of the electrolytic cell.
 Electrolysis is a useful method for the production of highly
reactive elements.
 The electrolytes used in the production of these metals are
molten salts rather than solutions of the salt in water.
 The electrochemical series shows that water is a stronger
oxidant than the metal ions for Na, K, Ca and Al.
 If water were present it would be reduced preferentially at
the cathode and no metal would form
 The use of a molten electrolyte usually involves greater
energy expenditure and greater wear on the cell.
 Sodium is extracted from molten sodium chloride by
electrolysis.
 A simple cell of molten salt is shown above. The electrodes
are made of an unreactive conducting material such as
graphite or platinum.
 The reaction occurring here is the reverse of the reaction
that occurs spontaneously between sodium and chlorine to
form sodium chloride.
 Electrical energy from the power supply has caused a non-
spontaneous reaction to occur
 At the cathode (-)
 The power supply pushes electrons towards this
electrode.
 Positive sodium ions accept electrons and become
sodium atoms:
Na+(l) + e- → Na(l)
 Sodium is solid at room temp, but is liquid at the
temperatures required to melt NaCl.
 It is less dense than molten NaCl and floats to the top of
the cell.
 At the anode (+):
 Electrons are withdrawn from this electrode by the
power supply.
 Since the electrode is made of unreactive material, the
electrode itself will not participate in an oxidation
reaction to supply electrons.
 Instead Cl- ions in the electrolyte give up electrons and
form chlorine atoms.
 These atoms quickly form molecules of Cl2 and bubbles
of chlorine gas form at the electrode.
2Cl-(l) → Cl2(g) + 2e-
 2Na+(l) + 2Cl-(l) → 2Na(l) + Cl2(g)
 Since Cl2 is a strong oxidant and Na is a strong
reductant, there must be no contact between them;
otherwise they will reform sodium chloride and the
products from the electrolysis will be lost.
 This will certainly occur in the simple cell.
 In order to produce sodium and chlorine
commercially, a modified cell, known as the Downs
cell has been developed to minimise contact between
the two products.
 A screen is used to prevent contact between the
chlorine gas formed at the anode and the sodium
formed at the cathode.
 Read about aluminium
on page 455
 We have seen that the oxide layer on the surface of
aluminium metal restricts further reaction of the
metal with other chemicals.
 The corrosion resistance and hardness of this layer can
be further increased by a process known as anodising.
 In this process, the oxide layer is made about 1000
times thicker by connecting the metal to the anode in
an electrolytic cell with sulfuric acid as the electrolyte.
 The thick oxide film that forms is easily dyed to give an
attractive appearance.
 Compared with cells using molten electrolyte such as
used to produce sodium and aluminium, electrolytic
cells using aqueous electrolytes tend to use less energy
and have lower operating costs.
 Have a read of pages 457 – 459 about the production of
chlorine and sodium hydroxide and the electrorefining
cell used for purifying copper metal.
 Page 459
 Question 8
 Page 460
 Question 9, 10, 13 – 15, 20 – 23, 25, 27, 29, 31
https://ssc12chem.wikispaces.com/file/view/Electrolysis.ppt