Section 1i: electrolysis

Electrolytes
1.48 understand an electric current as a flow of electrons or ions
1.49 understand why covalent compounds do not conduct electricity
1.50 understand why ionic compounds conduct electricity only when molten or in solution
1.51 describe experiments to distinguish between electrolytes and non-electrolyte.
n this topic we will study the effect of passing an electric current through a compound.
!n electric current is a flow of electrons. "or a substance to conduct electricity it must have mobile
charged particles i.e. electrons or ions. "or instance metals can conduct electricity #a current passes
through them$ because metals have delocali%ed electrons.
&ovalent compounds do not have any charged particles. 'hey consist of atoms or molecules which are
electrically neutral. 'hey cannot conduct electricity even if we melt or dissolve them in water #if they are
soluble that is$.
(n the other hand ionic compounds have charged particles #metal positive ions and negative non-metal
ions$. )owever* ionic compounds can only conduct when the ionic compound is molten or dissolved in
water. (nly in the li+uid or a+ueous state can the ions #charged particles$ move to the oppositely charged
electrode.
! li+uid #molten or solution$ that conducts electricity is called an electrolyte.
,e can tests substances if they are electrolytes or non-electrolytes #li+uids which do not conduct
electricity$ by doing simple tests.
! circuit is set up as shown below. t consists of a battery or power supply* wires* carbon electrodes and
an indicator of a current i.e. a bulb or an ammeter. &arbon is pic-ed as a material for the electrodes
because it is inert i.e. it does not react and does therefore not interfere in the electrolysis reaction. 'he
electrode which is connected to the positive terminal of the battery is named the anode. the electrode
connected to the negative one is the cathode.
'he substance to be tested is either molten or dissolved in water. f the bulb lights or a current is
measured by an ammeter* the substance tested is an electrolyte. n the diagram below the compound on
the left is ionic / the bulb is on - whilst the one on the right is covalent as the bulb does not light.
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Electrolysis
1.52 understand that electrolysis involves the formation of new substances when ionic compounds
conduct electricity
1.54 describe simple experiments for the electrolysis* using inert electrodes* of molten salts
such as lead#$ bromide
1.54 describe simple experiments for the electrolysis, using inert electrodes, of aqueous
solutions of sodium chloride, copper(! sulphate and dilute sulphuric acid and
predict the products
1.55 write ionic half-e+uations representing the reactions at the electrodes during electrolysis.
6ection 1i electrolysis 1 |
P a g e
molten or
dissolved
ionic
compound
(electrolyte)
covalent
compound
!n electrolyte is a different type of conductor than a solid metal. ,hen it conducts* the current passing
through the electrolyte causes a chemical reaction to ta-e place i.e. new substances are formed. 'he
ionic compound which ma-es up the electrolyte is decomposed. ! reaction in which a compound is
decomposed using an electrical current is called an electrolysis reaction. as a result new substances are
formed when an ionic compound conducts electricity. 'he current causes a chemical reaction converting
electrical energy into chemical energy.
7ou need to be able to predict the products of electrolysis reactions. 'o be able to do this you need to
-now0
what the ionic compound is
if it is molten or dissolved in water.
Electrolysis of molten ionic compounds or salts
,hen a molten salt is electroly%ed* the positive metal ions are attracted to the negative electrode or
cathode where they lose their charge as they gain electrons #reduction$ and become metal atoms. 'he
negative non-metal ions are attracted to the anode where they lose their negative charge. 'hey lose
electrons #oxidation$ and become non-metal atoms again and usually form molecules.
'his is shown by the example below which shows the electrolysis of molten lead bromide. 'he products
are bromine and lead.
'he actual changes going on at each electrode can be shown in ionic half e+uations0
Half equation at the cathode (-)
Pb2
+
(l) + 2e
-
Pb (s)
reduction
Half equation at the anode (+)
2r
-
(l) r2 (l) + 2e
-
o!idation
'he flow of charge is maintained in the following way0
by the flow of electrons in the wires and the electrodes and
by the movement of ions towards the oppositely charged electrode in the electrolyte.
When a molten salt is electrolyzed the metal is produced at the cathode whilst the non-metal is
formed at the anode.
Electrolysis of sodium chloride solution
6ection 1i electrolysis 2 |
P a g e
,hen a solution is electroly%ed predicting the products
becomes more complicated as also the water #the solvent$
also becomes involved. ,ater* although a covalent
compound* ioni%es a little bit producing hydrogen and
hydroxide ions which are also attracted to the electrodes. n
most cases a gas will be produced which needs to be
collected and tested. ,hen carrying out electrolysis during
which a gas will be produced the following set up ca be used
to collect the gas#es$.
6tarting
chemicals
concentrated sodium chloride solution or brine* 8a&l #a+$
ions present0
at cathode0 8a
9
)
9
at the anode0 &l
-
()
-

only 1 ion can react or be discharged at each electrode* the other remains in
solution
observations anode
bubbles* yellow green gas* nearly 101 ratio with gas at cathode
test0 gas bleaches damp litmus paper
cathode
bubbles* colourless gas
test0 :pop; sound with lit splint* more than 101 ratio
red litmus turns blue
products anode
chlorine is discharged and not the hydroxide ions which remain in solution
ionic half e+uation0 2&l
-
#a+$ &l2 #g$ 9 2e
-
< oxidation
cathode
hydrogen is discharged0
o ionic half e+uation0 2)
9
#a+$ 9 2e
-
)2 #g$ < reduction
sodium hydroxide 0 8a
9
and ()
-
are left in the solution as sodium hydroxide which can
be detected using an indicator
overall
e+uation
at anode0 2&l
-
#a+$ &l2 #g$ 9 2e
-
at cathode0 2)
9
#a+$ 9 2e
-
)2#g$
2)
9
#a+$ 92&l
-
#a+$ &l2 #g$9 )2 #g$
'rend0 for any concentrated solution of a salt made from a group 1 metal and a group = non-metal there
will always be three products0 #1$ hydrogen* #2$ the halogen* and #4$ the hydroxide of the group 1 metal.
Electrolysis of copper (! sulphate solution using inert electrodes
starting
chemicals
copper sulphate solution* &u6(4 #a+$
ions present0 at cathode0 &u
29
)
9
at the anode0 6(4
2-
()
-

observations anode
bubbles* colourless gas
test0 relights glowing splint
cathode
red deposit on electrode
products anode
oxygen is produced
ionic half e+uation0 4()
-
#a+$ (2 #g$ 9 2)2( #l$ 9 4e
-
< oxidation
sulphate* 6(4
2-
remains in solution
6ection 1i electrolysis " |
P a g e
cathode
copper
o is discharged and not the hydrogen ions as they remain in the solution0
o ionic half e+uation0 &u
29
#a+$ 9 2e
-
&u #s$ < reduction
hydrogen ions remain in solution
overall e+uation at anode0 4()
-
#a+$ (2 #g$ 9 2)2( #l$ 9 4e
-
at cathode0 2&u
29
#a+$ 9 4e
-
2&u #s$
4()
-
#a+$ 9 2&u
29
#a+$ (2 #g$ 9 2)2( #l$9 2&u #s$
Electrolysis of dilute sulphuric acid
'he two previous solutions are considered
concentrated solutions. 'he electrolyte*
sulphuric acid* in this example is diluted and this
also has an effect on -ind of products of the
electrolysis as none of the ions of the electrolyte
will be discharged. nstead they remain in the
solution. 'he ions which are discharged are the
hydrogen and hydroxide ions which form
hydrogen gas and oxygen gas.
n essence when a dilute solution is electroly%ed
water is decomposed. 'he identity and nature
of the electrolyte does not really matter
(abo"e image from http:##$$$.docbro$n.info#page%1#Exnd&hem#ExtraElectrochem.htm on '1#%(#'%1%!
starting
chemicals
dilute sulphuric acid* )26(4 #a+$
ions present0 at cathode0 )
9
at the anode0 6(4
2-
()
-

observations anode
bubbles* colourless gas*
volume approximately half of the gas produced at the cathode
test0 relights glowing splint
cathode
bubbles* colourless gas
volume0 twice as much as gas at the anode
test0 :pop; sound with lit splint*
products anode
oxygen is produced
ionic half e+uation0 4()
-
#a+$ (2 #g$ 9 2)2( #l$ 9 4e
-
< oxidation
cathode
hydrogen is discharged0
ionic half e+uation0 2)
9
#a+$ 9 2e
-
)2 #g$ < reduction
overall e+uation at anode0 4()
-
#a+$ (2 #g$ 9 2)2( #l$ 9 4e
-
at cathode0 4)
9
#a+$ 9 4e
-
2)2 #g$
6ection 1i electrolysis # |
P a g e
4()
-
#a+$ 9 4)
9
#a+$ (2 #g$ 9 2)2( #l$9 2)2 #g$
Electrolysis of copper solution using copper electrodes as used in the purification of copper.
cathode0
&u
29
#a+$ 9 2e
-

&u# s$
anode0
&u #s$ &u
29
#a+$
9 2e
-
(bservation
&opper ions from
solution are
deposited onto piece of
pure copper.
>ass of electrode
increases
(bservation
&opper from impure
copper goes
into solution. impurities
sin-.
>ass of electrode
decreases
Electrolysis calculations
1.5( recall that one faraday represents one mole of electrons
1.5( calculate the amounts of the products of the electrolysis of molten salts and aqueous
solutions
'he amount of product of an electrolysis reaction can be calculated and depends on0
'he amount of charge passed which is expressed in a number of faraday.
1 faraday = the charge of 1 mole of electrons = 96 500 coulombs (C)
'he amount of charge that passes in a circuit depends on the current #amperes or !$ of the circuit
and the amount of time #in seconds$ the current is switch on.
'he number of faraday can be calculated by0
o multiplying the amperes by seconds which gives coulombs #&$
o dividing the number of coulombs by 93 500 &
charge of the ions0 the greater the charge of the ion* the greater the number of electrons needed or
the greater the number of faraday
8a
9
9 e
-
8a this means that to produce 1 mole of sodium atoms #i.e.
24 grams$ one mole of electrons or 1 faraday is needed.
&a
29
9 2e
-
&a this means that to obtain 1 mole of calcium atoms two
moles of electrons or 2 faraday are needed.
2&l
-
#a+$ &l2 #g$ 9 2e
-
this means that to obtain 1 mole of chlorine molecules two
moles of electrons or 2 faraday are needed.
4()
-
#a+$ (2 #g$ 9 2)2( #l$ 9 4e
-
this means that to obtain 1 mole of oxygen molecules 4
moles of electrons or 2 faraday are needed.
,or-ed example
6ection 1i electrolysis $ |
P a g e
! solution of copper #$ sulphate is electroly%ed. )ow much copper will be deposited by a current of 2 !
flowing for 20 minutes?
6tep 10 calculate the amount of coulombs #<charge$
charge < 2 ! x 1200 seconds < 2400 &
6tep 20 calculate the number of faraday0
faraday < 2400193 500 < 0.025 faraday or number of moles of electrons
6tep 40 use ratio of redox e+uation &u
29
9 2e
-
&u
2 moles of electrons give 1 mole of copper atoms
0.025 moles of electrons give 0.0125 moles of copper atoms
0.0125 moles of copper < 34 x 0.0125 < 0.8g
Exercises
1. &omplete the table below
ion half e+uation number of faraday moles of substance mass #g$
8a
9
8a
9
9 e
-
8a
0.02 0.02 0.43
>g
29
>g
29
9 2e
-
>g
0.24
@r
-
2@r
-
#a+$ @r2 #g$ 9 2e
-
10
()
-
4()
-
#a+$ (2 #g$ 9 2)2( #l$ 9 4e
-
0.025
&l
-
2&l
-
#a+$ &l2 #g$ 9 2e
-
0.5
2. &opper #$ sulphate solution is electroly%ed for 15 minutes using copper electrodes and a 4 ! current.
&alculate the mass of copper produced.
4. !luminium oxide is extracted by electrolysis of molten aluminium oxide. 'he aluminium ion is !l
49
.
,hat mass of aluminium will be obtained if a current of 25000 ! flows for 24 hours?
4. ,hen sodium chloride is electroly%ed* the gases hydrogen and chlorine are obtained.
#a$ ,rite the e+uation for the formation of chlorine gas at the electrode
#b$ ! current of 2! is passed for 40 minutes. &alculate the volume of chlorine released at room
temperature and pressure.
5. 1-g of sodium is produced by electroly%ing sodium chloride. ,hat volume of chlorine is produced at
the same time?
3. Auring the electrolysis of lead #$ nitrate solution* lead is deposited at the cathode and oxygen at the
anode according to the e+uations below0
f a current of 0.450 ! flows for 1000 seconds calculate the mass of lead and volume of oxygen
6ection 1i electrolysis % |
P a g e
obtained at B'C.
cathode reaction0 Cb
29
9 2e
-
Cb
anode reaction0 4()
-
#a+$ (2 #g$ 9 2)2( #l$ 9 4e
-
6ection 1i electrolysis & |
P a g e