18. Electrolysis
Electrolysis can be easily carried out at home with 2 pencils, a short length of wire, and a 9 V battery.
What are the gases in the bubbles formed around the tip of the pencils?
Learning Outcomes
1. Describe electrolysis as the conduction of electricity by an ionic compound (an electrolyte), when molten and dissolved
water, leading to the decomposition of the electrolyte.
2. Describe electrolysis as evidence for the existence of ions.
3. Describe, in terms of the mobility of ions present and the electrode products, the electrolysis of molten sodium chloride,
using inert electrodes.
4. Predict the likely products of the electrolysis of a molten binary compound.
5. Apply the idea of selective discharge based on cations, anions and concentration effects using inert electrodes.
6. Describe the electrolysis of aqueous copper(II) sulfate with copper electrodes as a means of purifying copper.
7. Predict the products at the electrodes of the electrolysis of aqueous electrolytes, given relevant information.
8. Construct ionic equations for the reactions occurring at the electrodes during the electrolysis of given substances.
9. Describe the electroplating of metals.
10. Describe the production of electrical energy from simple electric cells.
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Electrolysis
Pre-Lesson Reading
1. What is Electrolysis?
cathode anode
electrode electrolyte
cation
anion
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Electrolysis
(3) At the anode (electrode connected to positive terminal), anions migrate to the anode, and are
oxidised when they donate electrons. The anion is discharged.
(4) The movement of ions in the electrolyte constitutes the flow of electric current.
Pre-Check 1
1. Two cells P and Q containing different liquids, were connected in series with a battery and a
suitable bulb, L, as shown in the diagram below.
(a) For which one of the following pairs of liquids did the bulb light up?
in P in Q
A concentrated hydrochloric acid hydrogen chloride in methylbenzene
B mercury dilute hydrochloric acid
C concentrated sodium chloride solution concentrated sugar solution
D copper(II) sulfate solution molten napthelene
E ethanol molten lead(II) bromide
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Electrolysis
Binary compounds contain only two elements, usually a metal cation and a non-metal anion. They
are usually ionic compounds. The cations and anions are discharged during electrolysis.
cathode
anode
In solid state, the ions are held in fixed positions in the crystal lattice by strong electrostatic forces
of attraction
Identify ions present: Na+(l) and Cl-(l)
When heated strongly, the electrostatic forces of attraction between the cations and anions are
broken, and the ions are free to move and no longer held in fixed positions.
Identify electrodes used: carbon
Carbon is an inert electrode. Inert electrodes do not react with the products of electrolysis or
the electrolyte, and are not involved in the electrolysis process.
At the anode (electrode connected to the At the cathode (electrode connected to the
positive terminal of the battery) negative terminal of the battery)
Cl ions are attracted to the anode. Na+ ions are attracted to the cathode.
Each Cl ion lose 1 electron to the anode to Each Na+ ion gain 1 electron from the
form a chloride atom. cathode to form a sodium atom.
2 Cl atoms come together to form Cl2 gas Na+ ions are reduced.
Cl ions are oxidised. Na+ ions are discharged as sodium metal.
Cl ions are discharged as chlorine gas.
Na+(l) + e- Na(l)
2Cl (l) Cl2(g) + 2e -
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Electrolysis
Checkpoint 1
The diagram shows an electrolysis tank used industrially to produce aluminium from aluminium
oxide.
(a) Explain why the aluminium oxide ore has to be heated until molten.
(b) Construct ionic equations for the reactions which take place at the electrodes.
(d) Carbon is an inert electrode but for the electrolysis of aluminium oxide, they need to be replaced
regularly. Suggest a reason why.
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Electrolysis
When aqueous solutions are involved, ions compete to be discharged at the electrodes.
(2) Anion – ease of discharge follows the series below. The larger anions are more stable and
less likely to be discharged.
(3) Concentration – higher concentrations can affect which ion is preferentially discharged (see
electrolysis of concentrated sodium chloride solution or brine).
(4) Electrodes – Reactive electrodes participate in the electrolysis reaction; inert electrodes do
not participate in the electrolysis reaction.
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Electrolysis
Cations Anions
From sodium chloride Na+(aq) Cl(aq)
From water H+(aq) OH(aq)
Step 2: Determine ion preferentially discharged at the cathode (electrode connected to negative
terminal of battery)
Step 3: Determine ion preferentially discharged at the anode (electrode connected to positive terminal
of battery)
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Electrolysis
Overall
electrolysis
2H2O(l) 2H2(g) + O2(g)
As electrolysis proceeds, concentration of sodium chloride will increase. This would affect the
products formed during electrolysis after some time.
Cations Anions
From sodium chloride Na+(aq) Cl(aq)
From water H+(aq) OH(aq)
Step 2: Determine ion preferentially discharged at the cathode (electrode connected to negative
terminal of battery)
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Electrolysis
Na+(aq) remains in solution. (Metal ions are never discharged from aqueous solutions.)
Step 3: Determine ion preferentially discharged at the anode (electrode connected to positive terminal
of battery)
Checkpoint 2
The diagram represents an experiment in which an electric current is passed through concentrated
hydrochloric acid.
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Electrolysis
(a) Give the names and formulae of all the ions present in this solution. Explain what happens to
each of these ions as it arrives at an electrode. Write ionic equations for the reactions at the
electrodes.
(b) Identify the gases collected in the inverted test tubes and suggest how they can be identified.
(c) Why would steel not be a suitable material for the anode?
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Electrolysis
Cations Anions
From sulfuric acid H+(aq) SO42(aq)
From water H+(aq) OH(aq)
Step 2: Determine ion preferentially discharged at the cathode (electrode connected to negative
terminal of battery)
Step 3: Determine ion preferentially discharged at the anode (electrode connected to positive terminal
of battery)
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Electrolysis
Overall
electrolysis
2H2O(l) 2H2(g) + O2(g)
The electrons on both sides of the two equations must cancel each other out.
Checkpoint 3
The diagram represents an experiment in which an electric current is passed through dilute sulfuric
acid.
(a) Give the formula of all the ions present in this solution. Construct an ionic equation for the
reaction at each electrode.
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Electrolysis
(c) Suggest why the volume of hydrogen collected is twice as much as the volume of oxygen
collected.
Cations Anions
From copper(II) sulfate Cu2+(aq) SO42(aq)
From water H+(aq) OH(aq)
Step 2: Determine ion preferentially discharged at the cathode (electrode connected to negative
terminal of battery)
Step 3: Determine ion preferentially discharged at the anode (electrode connected to positive terminal
of battery)
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Electrolysis
Overall
Cations Anions
From copper(II) sulfate Cu2+(aq) SO42(aq)
From water H+(aq) OH(aq)
Step 2: Determine ion preferentially discharged at the cathode (electrode connected to negative
terminal of battery)
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Electrolysis
Step 3: Determine ion preferentially discharged at the anode (electrode connected to positive terminal
of battery)
However, the copper anode participates in the electrolysis process. It is known as a reactive
electrode.
The copper electrode is oxidised into Cu2+(aq) ions which enter into the electrolyte solution.
Overall
The concentration of Cu2+(aq) in the solution remains unchanged as Cu2+(aq) deposited as Cu(s)
at the cathode is continuously replenished by the anode.
The intensity of the blue colour remains unchanged until the anode disappears.
Checkpoint 4
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Electrolysis
A pupil electrolysed 2 dm3 of aqueous copper(II) sulfate using platinum electrodes. A current of 1
ampere was passed. The graph of gain in mass of the cathode against time is plotted below.
(a) Write ionic equations, including state symbols, to represent the formation of:
(i) Copper at the cathode
(ii) Oxygen at the anode
(b) The solution initially contained 25.0 g of copper(II) sulfate crystals (CuSO4.5H2O).
(i) Calculate the initial concentration of the copper(II) sulfate solution in mol/dm3.
(ii) From the graph, what mass of copper was deposited after 10 minutes? How many
moles of copper is this?
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Electrolysis
(iii) What is the concentration of the copper(II) sulfate solution, in mol/dm3, after 10
minutes?
(iv) If the electrodes were replaced by copper electrodes, what would be the concentration
of the copper(II) sulfate solution in mol/dm3 after 10 minutes?
(c) Describe the appearance of the aqueous copper(II) sulfate using the platinum electrodes:
(i) After 5 minutes
(ii) After 40 minutes
(d) Why does the mass of copper deposited at the cathode not increase after 32 minutes, although
the volume of oxygen given off at the anode continues to increase after this time?
(e) Theoretically, 0.64 g of copper should have been deposited on the cathode after 32 minutes.
Suggest a reason why only 0.60 g of copper were deposited.
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Electrolysis
4.2 Electroplating
Electroplating is the process of depositing a thin layer of metal on another object by electrolysis.
Allows coating of a metal object with another metal to give it an attractive appearance, or to protect
the metal below.
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Electrolysis
- Copper from the electrolyte is deposited on the object, while copper from the anode replaces
the Cu2+(aq) in the electrolyte.
Checkpoint 5
chromium
(a) Add in the positive and negative signs to the power source to allow the object to be plated.
(b) Describe what happens to the electrolyte and the chromium metal.
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zinc electrode
copper
electrode
dilute sulfuric acid
Step 1: Identify which electrode is oxidised. Reduction will occur at the other electrode.
The more reactive metal will be oxidised. In this case, Zn is more reactive than Cu. Hence Zn is
oxidised.
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Electrolysis
Zinc atoms are oxidised. They give up The electrons from the zinc electrode travel
electrons to form zinc ions. to the copper electrode.
The zinc ions enter into solution. H+(aq) accepts the electrons and is reduced
to form hydrogen gas.
zinc electrode
copper
electrode
aqueous copper(II) sulfate
copper deposited on the
positive electrode
Step 1: Identify which electrode is oxidised. Reduction will occur at the other electrode.
The more reactive metal will be oxidised. In this case, Zn is more reactive than Cu. Hence Zn is
oxidised.
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Electrolysis
Enrichment: A slightly more complicated zinc-copper cell connected with a simple salt bridge.
5.3 What Affects the Voltage Reading for Simple Electric Cells?
No current will flow if the two electrodes are made of the same
metal. Why?
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Electrolysis
Checkpoint 6
1. The circuit shown below is set up and an electric current is passed through the four cells in
series.
In which cells is the intensity of the blue colour of the solution unchanged?
2. In the diagram, each cell contains an aqueous solution of a single salt and all four electrodes
are platinum. Electrodes Q and S increase in mass during the electrolysis but no gas is given
off at Q or S.
If the increase in mass of Q is greater than that of S in the same time, which statement must
be true?
A. The cation of the solution in cell 1 is different from the cation of the solution in cell 2.
B. The current flowing in cell 1 is greater than the current flowing in cell 2.
C. The cation in cell 1 is the same as in cell 2 but the solution in cell 1 is more concentrated
than in cell 2.
D. The loss of mass of electrode P is less than the loss of mass of electrode R.
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Electrolysis
3. A strip of moistened filter paper is laid on a microscope slide. A drop of silver nitrate solution
is placed near one end of the paper and a drop of potassium iodide solution is placed near the
other end. Using inert electrodes, the apparatus is connected to a suitable d.c. power supply.
After some time, a pale yellow streak appears as shown in the diagram.
(a) Give the formulae of the ions present in the solutions of silver nitrate and potassium iodide.
(b) Name the compound responsible for the pale yellow streak and write the ionic equation for
its formation.
(c) Explain the process leading to the formation of the streak and explain why the streak
appears nearer the cathode than the anode.
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