Electrolysis

Order of Reactivity of Metals & H⁺ in Electrolysis

(Determines which ions discharge first at the cathode)
Ion Reactivity Discharge Preference Product Formed
K⁺ Very High Never discharged H₂ (from water)
Na⁺ High Never discharged H₂ (from water)
Ca²⁺ High Never discharged H₂ (from water)
Mg²⁺ High Never discharged H₂ (from water)
Al³⁺ High Never discharged H₂ (from water)
Zn²⁺ Moderate Only if concentrated Zn or H₂
Fe²⁺ Moderate Only if concentrated Fe or H₂
Discharges if metal is more
H⁺ Reference H₂ (gas)
reactive than H
Pb²⁺ Low Discharged before H⁺ Pb (metal)
Cu²⁺ Low Always discharged Cu (metal)
Ag⁺ Very Low Always discharged Ag (metal)
Au³⁺ Minimal Always discharged Au (metal)
Metal ions discharged from low reactivity to high reactivity. Low reactivity metal discharge first. High reactivity
prefers to be at ion form.

Rules for Discharge in Aqueous Solutions:

1. At the Cathode (-):
o If the metal ion is more reactive than H⁺ (e.g., K⁺, Na⁺, Ca²⁺, Mg²⁺, Al³⁺), H₂ gas forms instead
2H++2e−→H2
o If the metal ion is less reactive than H⁺ (e.g., Cu²⁺, Ag⁺, Au³⁺), the metal ion discharges
Cu2++2e−→Cu
At the Anode (+):
o If halide ions (Cl⁻, Br⁻, I⁻) are present, they discharge first
2Cl−→Cl2+2e−
o Otherwise, OH⁻ (from water) discharges, forming oxygen gas
4OH−→O2+2H2O+4e−
2. Why H⁺ is special?
o H⁺ is not a metal ion, but it competes with metal ions for discharge.
o Its position in the reactivity series determines whether metals or H₂ gas forms.
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Electrolysis Questions
1. Electrolysis of Molten Lead Bromide

a) The bulb will not light until the lead bromide has melted. Why not?
b) What will be seen at the anode?
c) Name the substance in (b).
d) What will be formed at the cathode?
e) write the half equation at the cathode and anode.
d) Name which is oxidation which is reduction.

2. Six substances A to F were dissolved in water, and connected in turn into the circuit below. A represents an
ammeter, which is used to measure current. The table shows the results.

Substance Current (A) At Cathode (-) At Anode (+)

A 0.8 Copper Chlorine
B 1.0 Hydrogen Chlorine
C 0.0 —————— ———————
D 0.8 Copper Oxygen
E 1.2 Hydrogen Oxygen
F 0.7 Silver Oxygen
a) Which solution conducts best?
b) Which solution is a non-electrolyte?
c) Which solution could be:
i) Silver nitrate?
ii) Copper(II) sulfate?
iii) Copper(II) chloride?
iv) Sodium hydroxide?
v) Sugar?
vi) Concentrated hydrochloric acid?
d) Explain how the current is carried:
i) Within the electrolytes.
ii) In the rest of the circuit.

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 3. The electrolysis below produces gases A and B.

a. Why does the solution conduct electricity?

b. Identify each gas.
c. Write the half-equations to show how the two gases are produced
d. Write the redox
e. The solution remaining after the electrolysis will turn litmus paper blue.
i. What is the name of this solution?
ii. State one chemical property for it

4. Here is a list of ions in electrolysis:

a) List the ions that are present in concentrated solutions of list the ions present in:
i. Sodium chloride solution.
ii. Copper(II) chloride solution.
b) Explain how/why ions move during electrolysis (using Pt electrodes).
c) Write half-equations for the reaction at:
i. Anode
ii. Cathode
d) Why are the anode reactions the same for both solutions?
i. Why would the anode reactions differ if solutions were very dilute?
ii. Write the new anode half-equations.
e) Why is copper obtained at the cathode, but sodium is not?
f) Name another solution that produces the same products as concentrated NaCl.

5. Molten lithium chloride contains lithium ions (Li 1) and chloride ions (Cl 2).

Draw ion/electron movement diagrams.

i. the ions move when the switch is closed
ii. the electrons flow in the wires
Write electrode reactions and the overall reaction. Write the oxidation and reduction.

6. Dilute Aqueous Lithium Chloride Electrolysis

a. Give the names and symbols of the ions present.
b. Say what will be formed, and write a half equation for the reaction:

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 i. at the anode
ii. at the cathode
c. Name another compound that will give the same products at the electrodes.
d. How will the products change, if a concentrated solution of lithium chloride is used

7. An experiment is needed, to see if an iron object can be electroplated with chromium.

a. Suggest a solution to use as the electrolyte.
b. Draw a labelled diagram of the apparatus that could be used for the electroplating.
c. Show how the electrons will travel from one electrode to the other.
d. Write half-equations for the reactions at each electrode.
e. At which electrode does oxidation take place?
f. The concentration of the solution does not change. Why not?

8. Nickel(II) sulfate (NiSO4 ) is green. A solution of this salt is electrolysed using nickel electrodes.
a. Write a half-equation for the reaction at each electrode.
b. At which electrode does reduction take place? Explain your answer
c. What happens to the size of the anode?
d. The colour of the solution does not change, during the electrolysis. Explain why.
e. Suggest one industrial use for this electrolysis

1. Basic Concepts
1. Define electrolysis and state the purpose of an electrolyte.
2. Explain the difference between the anode and cathode in terms of:
a) Charge
b) Reaction type (oxidation/reduction)
3. Why do solid ionic compounds not conduct electricity, but molten or dissolved ones do?

2. Electrolysis of Molten Compounds

4. Lead(II) iodide (PbI₂) is electrolyzed in its molten state.
a) Write the half-equations for the reactions at each electrode.
b) Predict the products formed at the anode and cathode.

3. Electrolysis of Aqueous Solutions

6. A dilute solution of sulfuric acid (H₂SO₄) is electrolyzed using inert electrodes.
a) List all ions present in the solution.
b) Write the half-equations for the reactions at each electrode.
c) Identify the gases produced at each electrode.
7. Predict the products of electrolysis for a concentrated solution of copper(II) chloride (CuCl₂).
a) Write the half-equations.
b) How would the products differ if the solution were very dilute?

4. Reactivity Series & Selective Discharge

8. A solution contains sodium ions (Na⁺) and silver ions (Ag⁺). During electrolysis, which ion is discharged at the
cathode? Explain your answer.
9. During the electrolysis of brine (concentrated NaCl), chlorine gas is produced at the anode instead of oxygen.
Why?

5. Experimental & Observational Questions

13. In an electrolysis experiment, a student observes bubbles at both electrodes.
a) What tests could be used to identify the gases produced?
b) If the electrolyte was dilute sodium hydroxide (NaOH), predict the gases formed.
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 14. During the electrolysis of water, why is the volume of hydrogen gas collected twice that of oxygen gas?

6. Aqueous potassium nitrate

15. Aqueous potassium nitrate (KNO₃) is electrolyzed.
a) Why are no metal ions discharged at the cathode?
b) Write the half-equations for the reactions at each electrode.
16. Explain why the mass of the anode decreases during the electrolysis of copper(II) sulfate using copper
electrodes, but remains unchanged when using platinum electrodes.

7. Dilute Hydrochloric Acid (HCl) Electrolysis

a) List all ions present in the solution.
b) Write the half-equations for the reactions at each electrode.
c) Identify the gases produced at each electrode.

8. Concentrated Potassium Iodide (KI) Solution

a) Predict the products at the anode and cathode.
b) Write the half-equations.
c) How would the products change if the solution were very dilute?

9. Sodium Sulfate (Na₂SO₄) Solution

a) Identify the ions present.
b) Explain why hydrogen gas (not sodium) forms at the cathode.
c) What gas forms at the anode? Write the half-equation.

10. Mixed Ions in Solution

A solution contains:
 Potassium ions (K⁺)
 Zinc ions (Zn²⁺)
 Copper ions (Cu²⁺)
a) Which ion is discharged at the cathode? Explain.
b) What forms at the anode if the solution contains bromide ions (Br⁻)?

11. Electrolysis of Dilute vs. Concentrated Solutions

a) Why does concentrated sodium bromide (NaBr) produce bromine (Br₂) at the anode, but dilute NaBr produces
oxygen (O₂)?
b) Write the half-equations for both cases.

12. Competing Ions

A solution contains:
 Silver ions (Ag⁺)
 Iron(II) ions (Fe²⁺)
 Hydrogen ions (H⁺)
a) Which ion is discharged first at the cathode? Justify using the reactivity series.
b) What would form at the anode if sulfate ions (SO₄²⁻) are present?

13. pH Changes During Electrolysis

a) Explain why the pH of a dilute sulfuric acid (H₂SO₄) solution increases during electrolysis.
b) Write the overall reaction.