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Electrolysis of molten compounds  Electrode connected to the positive terminal of the cell

is positive electrode and is given a name, anode.


 The electrode connected to the negative terminal of
the cell is negative electrode and is called the cathode.

 When electricity is passed through an electrolyte,


chemical reaction happens.
 In this reaction, chemical is splitting up into 2 new
substances.
 All electrolytes are ionic, which means they are
composed of positively and negatively charged ions.
2 types of electrochemical cell:  On passing an electric current through the electrolyte,
a) Electrolytic Cell these ions move towards the oppositely charged
b) Voltaic Cell /Galvanic Cell electrode.

 Electrolysis cell : Electricity energy  Most negatively charged ions are non-metal ions, such
chemical energy as oxide (O2-, chloride (Cl-), Iodide (I-), etc.
 Voltaic cell : Chemical energy electricity  During electrolysis, negatively charged ions move
energy towards the positive electrode(anode). The negative ions
lose their electron(s) to the anode, which is positively
The Electrolytic Cell charged.
 The electron(s) is then move to the cathode through
the external circuit (the wire).
 The positively charged ions move towards the
negative electrode(cathode').
 These positive ions are metal ions, such as copper
(Cu2+), silver (Ag+), lead (Pb2+), etc, or hydrogen (H+).
 At cathode, positive ions gain electron(s) from the cathode to the anode and hence allows conduction of
cathode, which has an excess of electrons and therefore electricity.
an overall negative charge.  During the electrolysis, electrical energy is supplied to
the system to produce a chemical reaction.
 This process results in the chemical decomposition of  Therefore, during electrolysis, electrical energy convert
the electrolyte. It also allows electrons to travel from the into chemical energy.
 Example 1:Electrolysis of MOLTEN Lead (II) Bromide

Observation Observation
When electricity is
 When
flowing, a silvery
electricity is
deposit of lead metal
flowing, brown
forms on the
fumes of
cathode. In fact, as it
bromine gas are
is molten, it is more
seen at the
likely to drip off in a
anode.
molten blob.
 This is composed of lead(II) ions, Pb2 + , and bromide
Half equation Half equation
ions, Br-. Its chemical formula is therefore PbBr2.
Pb2+ + 2e ---> Pb 2Br- ---> Br2 + e
 A suitable apparatus which could be used to carry out
this electrolysis is shown in Figure above. Explanation Explanation
 The bulb helps to show when electricity is flowing in
the circuit, and until the lead(II) bromide is completely  The lead(II)  The bromide
molten, the bulb does not light up . This confirms that ions, as they are ions, as they are
electrolytes have to be molten for the ions to start to move positive, move to negative, move
to the electrodes and thereby conduct electricity. the negative to the positive
At the Cathode At the Anode cathode, where anode, where
each ion gains each loses an
 We have learnt that electrolyte can be molten ionic
two electrons to electron to form compound or aqueous solution of ionic compound, acid or
form a lead atom. a bromine atom. alkali.
 Any reaction  Then two of  An aqueous solution is solution of water of a
at a cathode these newly substance. For example, if you heat sodium chloride until
involved is again formed atoms it melts, it is called molten sodium chloride, but if you
in electrons. This combine to form dissolve sodium chloride in water, it is called aqueous
is called bromine gas. sodium chloride.
reduction or more  Any reaction  Electrolysis of aqueous solution is different from
exactly, cathodic at an anode electrolysis of molten electrolyte.
reduction . involves a loss  This is mainly because an aqueous solution contain
of electrons. more types of ions.

 In summary, the lead(II) bromide is split into its  Let us take the example of molten sodium chloride and
component elements : sodium chloride aqueous.
 In molten sodium chloride, the ion present are sodium
PbBr2 ---> Pb + Br2
ion (Na+) and chloride ion (Cl-), due to the decomposition
of the solid sodium chloride.
NaCl ---> Na+ + Cl-

 In sodium chloride aqueous, other than the


decomposition of sodium chloride solid to form
sodium and chloride ions, some of the water
molecule will also disassociates to form hydrogen
(H+) and hydroxide (OH-) ions.
Electrolysis Of Molten Lead(II) Oxide
NaCl ---> Na+ + Cl-
(electrolysis of aqueous solutions)
H2O ---> H+ + OH-
Introduction
 Which means in an aqueous solution, it can be
more than 1 positive and negative ions.
 When the ions move to the anode and cathode,
only 1 negative ion and 1 positive ion will be
selected to be discharged, and this is called
selective discharge.
 There are a few factors that determine which ion
will be selected to be discharge, and this will be
discussed in next section.

Factors Affecting Electrolysis

The chart above lists the ions in order of difficulty of


 There are three main factors that can affect the
discharge.
electrolysis products, there are:
The ions at the top of the list is more difficult to be
discharged, but as we go down the table, they
1. position in the electrochemical series
become easier to be discharged. For example, Cu 2+
2. the concentration and
easier to be discharged compare with H + and OH- is
3. the type of electrode
easier to be discharged compare with I -.
Electrochemical series
This series of ions is called the Electrochemical
Series. The lower the ion in the electrochemical
series, the easier the ion to be discharged during
electrolysis.

Electrolysis of Aqueous Sulphuric Acid


As sulphuric acid is aqueous, it is composed not
only of hydrogen ions (H+ ) and sulphate ions
(SO42-), but also of hydroxide ions (OH-) from the
water.
H2SO4 + H2O --> 2H+ + SO42- + H+ + OH- molecule .

The apparatus used to carry out this electrolysis Equation: Equation:


and collect the gases given off is shown in Figure 2H+ + 2e ---> H2 OH- + 4e ---> O2 + H2O
9 .8 .
Notes
 When we have more than one type of ion moving
to an electrode, selective discharge (or  With electrolysis of aqueous solutions of
preferential discharge) takes place. dilute acids or alkalis, the volume of
 This means that the ion which can lose or gain hydrogen given off at the cathode is roughly
electrons with the greatest ease is discharged, twice that of the oxygen gas at the anode.
and the other ions, which are harder to  Accordingly, the elements of water are
discharge, remain in solution . lost and as the electrolysis continues, the
 With the electrolyte aqueous sulphuric acid, concentration of the acid or alkali
migration of ions to the electrodes also occurs. increases .
At the Cathode At the Anode  Essentially, the electrolysis of aqueous
sulphuric acid is the electrolysis of water,
 Here we have  Here we have a with hydrogen and oxygen gas being given
only one ion, the choice of either off in a ratio of 2 : 1 .
hydrogen, H+ (aq), sulphate, SO42-
[edit] Concentration
and each ion gains (aq), or hydroxide
an electron to OH- (aq) ions.
 If the concentration of a particular ion is high, it
become a  Hydroxide is will be selected to be discharged even though it
hydrogen atom. easier to discharge, is higher in the electrochemical series compares
 Two of these so oxygen gas is with another ion present in the solution.
newly formed given off at the
 For example, if dilute hydrochloric acid is
atoms then anode.
electrolysed, hydrogen gas is given off at the
combine to form a
cathode and oxygen gas at the anode.
hydrogen gas
 However, when concentrated hydrochloric acid is hydrogen ions
electrolysed, hydrogen gas is still given off at the move to the chloride ions (Cl-)
cathode, but chlorine rather than oxygen gas will cathode . and the hydroxide
be released at the anode, even though chloride ions (OH-) migrate
 As the hydrogen
is in a higher position in electrochemical series. to the anode .
ion (H+), is lower in
Electrolysis Of Diluted Or Concentrated the reactivity series  The chloride
Hydrochloric Acid than the sodium ions (Cl-) are
ions (Na+ ), it preferentially
accepts electrons discharged
more easily. because of their
 The hydrogen higher
ions (H+) are concentration
discharged.

Equation: Equation:
H+ + e ---> H Cl- ---> Cl + e

Hydrogen atoms join in Chlorine atoms join in


pairs to give pairs to give
molecules : molecules:
Electrolysis of Concentrated Sodium Chloride
H + H ---> H2 Cl + Cl ---> Cl2
Solution (Brine)
The electrolytic cell used for electrolysis of Changes in Solution
concentrated sodium chloride solution is designed to
collect gaseous products at both electrodes as  As the hydrogen ions and chloride ions
shown in Figure above. are discharged, sodium ions and hydroxide
At Cathode At Anode ions remain in the solution . The solution
becomes sodium hydroxide .
 The sodium and  Both the
Type of Electrode Electrolysis of Copper(II) Sulphate by Using
Copper Electrode
 This is best shown if we consider the electrolysis
of aqueous copper(II) sulphate solution.  However, if we use copper electrodes, these are
active electrodes and do affect the electrolysis.
Electrolysis of Copper(II) Sulphate by Using Anode At the anode, the copper electrode dissolves
Carbon Electrode into solution :
Anode Partial equation Cu(s)  Cu 2+ (aq) + 2e (copper
electrode dissolves )
1. If we use carbon electrodes, they are inert
Cathode At the cathode, the copper ions are
electrodes and do not affect the electrolysis .
deposited as pink copper metal:
2. Therefore, at the anode, we have a choice of
sulphate or hydroxide ions . Partial equation Cu2+ (aq) + 2e-  Cu (s) (copper
3. The hydroxide ions are easier to discharge, metal deposited)
so oxygen gas is given at the anode : Evaluating electrolysis in industry
Partial equation 40H- (aq)  O2(g) + 2H2O (l) +
4e- (oxygen gas given off)
[edit] Industrial Applications of Electrolysis
Cathode
 Electrolysis has many varied industrial applications.
 At the cathode, we have a choice of copper or  The major applications of electrolysis in industry are
hydrogen ions .
 The copper ions are easier to discharge, so we 1. Extraction of Metals
see a pink deposit of copper metal on the carbon 2. Purification of Metal
electrode. 3. Electroplating
Partial equation Cu2+ (aq) + 2e-  Cu (s) (copper
metal deposited)

[edit] Extraction of Metal


 The extraction of metals from their ores, in particular  Silver (Ag) and gold (Au) need no extraction because
aluminium and sodium, is important industrial uses of they exist as element in nature.
electrolysis.  Those metals which are more reactive than carbon are
 The diagram below shows the methods of extraction extracted by electrolysis.
for different metals.

[edit] Extraction of Aluminium

 Aluminium is the most abundant metal found in the


earth's crust. It makes up about 8% by weight of the
Earth’s solid surface.
 It is also a very useful metal due to its low density and
ability to resist corrosion.
 The main source of aluminium is bauxite ore
(Aluminium Oxide).
 In industry, aluminium is extracted by electrolysis from
bauxite ore.

 We can see that those metals which are less reactive


than carbon in reactivity series are extracted from their
ore by displacement reaction using carbon. This will be
discussed in detail in chapter 3, form 5, Oxidation and
Reduction.
 Copper and mercury can be extracted from their ore
by burning directly in air. Adding Cryolite
 In electrolysis, molten aluminium oxide must be used  Also, this cell uses large quantities of
to extract aluminium. Aluminium oxide decompose to form electricity, and therefore needs cheap
aluminium and oxide ions when melted. sources of power.
Al2O3 ---> 2Al3+ + 3O2- [edit] Extraction of sodium chloride

 However, the melting point of aluminium oxide is very


high (over 2 000°C), so another aluminium compound
called cryolite (Na3AIF6) is added to lower down the
melting point (about 980oC).

 The diagram above shows how aluminium is extracted


from molten aluminium oxide by electrolysis.
 Graphite is used as the anode and cathode.
 During electrolysis, the aluminium ions are attracted
towards the graphite cathode.
 The ions is discharged and become molten aluminium
metal.
 In industry, sodium is extracted from molten
 The partial equation of this reaction is as follow:
sodium chloride. Molten sodium chloride is
Al3+ + 3e ---> Al
put into the apparatus as showing in the
 At the anode, oxygen gas which also has diagram above.
commercial value is collected. The partial  When sodium chloride is melted, the sodium
equation of this reaction is as follow: and chloride ions disassociate to become
2O2- ---> O2 + 4e freely move ions, as shown in the chemical
equation below.
NaCl ---> Na+ + Cl-
 At the temperature of 980 °C, the oxygen
burns the carbon anode. Therefore the
anode has to be replaced periodically.
 In thhis electrolytic cell, graphite was
used as anode while iron is used as
cathode.
 The negative chloride ions are attracted
to the anode and then discharged to
form chlorine gas.
2Cl- ---> Cl2 + 2e

 Since chlorine gas is also


significant in industry, it is collected  In the refining or purification of
and stored. copper, the impure copper is made the anode and a thin,
 In cathode, the sodium ions are pure copper plate is used as a cathode.
discharged to form sodium atom.  The electrolyte is usually acidified copper(II) sulphate
+
Na + e ---> Na solution.
 When electricity flows, the
 Due to high temperature, the copper dissolves from the
sodium metal formed is in impure anode and goes into
molten form. solution as copper ions.
 Metal sodium have lower  Impurities in the copper do not
density. Therefore it moves dissolve, and instead fall off
upward and been collected. the anode as anode sludge. At
[edit] Purification Of Copper the cathode, the copper ions
are deposited as pure copper
metal.
Reaction in anode (impure form a thin protective
copper) coating of a metal on
In anode, the copper atoms from the surface of another
the electrode are ionised to form which is likely to
copper(II) ions. corrode.

Cu ---> Cu2+ + 2e  The diagram above


illustrate the
Reaction in cathode (pure
electroplating of a key
copper)
with copper.
Cu2+Cu ---> Cu + 2e
[edit] Electroplating  In this process, we
need to make the
cathode the object for
plating (the key.
 The anode is then
made of the metal we
wish to plate with
(copper), and the
electrolyte needs to
be a solution of a salt
of this metal
(copper(II) sulphate).
Anode
Electroplating: Coating
with a Thin Protective
 In anode, the copper
Layer of Metal
atoms from the
electrode are ionised
 A very common use
to form copper(II)
of electrolysis is to
ions.
Cu ---> Cu2+ + 2e
Cathode

 In cathode, the
copper ions are
discharged to
form copper
atom and then
deposit on the
surface of the
key
Cu2+ ---> Cu + 2e

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