Chapter 7

Electrolysis

Notes Chemistry O.L 2025 72 Dr Peter Alfred

 Chapter seven

Electrolysis

 Electrolysis is: “the breakdown of an ionic compound, molten or in

aqueous solution, by the passage of electricity”

 The decomposition of
molten lead bromide
occurs using the apparatus
above. A current is passed
through graphite rods
called electrodes. A liquid
that conducts current is
called an electrolyte.
 The negative terminal is attached
to one rod, which becomes the
negative electrode, the cathode.
 The positive terminal is attached to the other rod.
This becomes a positive electrode, the anode.

Note: The compound must be molten to allow the charged ions to flow.
You cannot carry out electrolysis on solid lead bromide.

 Cations: are positive ions that go to the negative electrode, the cathode.

 Anions: are negative so go to the positive electrode, the anode.

Electrolysis is a redox reaction. Reduction takes place at the cathode and

oxidation at the anode.

Notes Chemistry O.L 2025 73 Dr Peter Alfred

How to construct half ionic equation (very important):

1- You have to consider the following:

 PANIC (positive anode negative is cathode).
 OILRIG (Oxidation is loss of electrons; Reduction is
gaining of electrons).
 RAC (Reduction at cathode)/OAA (Oxidation at Anode).
 7 diatomic elements (N2 / O2 / H2 / F2 / Cl2 / Br2 / I2).

Note: F2 / Cl2 / Br2 / I2 are poisons gases so you must use them
in a fume cupboard.

A- Molten compounds: (after decomposition)

1- The first one is a positive ion goes to the cathode where Reduction
occurs changing to a metal
2- The second one is a negative ion goes to the anode where Oxidation
occurs changing to a non- metal
3-Electrolyte is used up.
How does lead bromide decompose?

 At the cathode: molten

lead is formed:

Pb 2+
(l) + 2e → Pb (l)
-

 At the anode: gaseous

bromine is evolved:

2Br -
→ Br2(g) + 2e -

 Electrolyte is used up

Notes Chemistry O.L 2025 74 Dr Peter Alfred

 Examples: (Electrolysis of Molten sodium chloride)

Some Solved examples:

Molten Anode +ve electrode Cathode –ve electrode

Sulfur Sodium
Sodium sulfide S2- S +2e- Na+ + e- Na
Aluminum Oxide Oxygen Aluminum
2O 2-
O2 + 4e -
Al + 3e
3+ -
Al
Lithium Phosphide Phosphorus Lithium
P 3-
P + 3e -
Li + 1e
+ -
Li
Iron III Iodide Iodine Iron III
2I -
I2+ 2e -
Fe + 3e
3+ -
Fe

The electrolysis of solutions:

When a salt is dissolved in water, its ions become mobile.
Hence, the solution can be electrolyzed. However, the products from
the salt solution will be different to the molten solution because of
the presence of the water, which itself produces ions.

During electrolysis, these ions compete with the metal and non-metal
ions from the dissolved salts, to receive or give up electrons.

Notes Chemistry O.L 2025 75 Dr Peter Alfred

So which will evolve (will be discharged)?

At the cathode:(less reactive ion goes to the cathode)

The more reactive a metal is

the more it prefers being ions.

Therefore, if a reactive metal

such as zinc or magnesium is
present it will remain as the
ions. The H ions will accept the
+

electrons and hydrogen gas will

be given off at the cathode.

If a less reactive metal, such as

copper or silver is present it would rather accept the electrons than
H+. Hence, the metal forms at the cathode.

Very important note:

At the anode:

If halide ions are present, Cl , Br , I , they will give up their electrons to

- - -

become molecules of Cl2, Br2 and I2 respectively (concentrated solutions).

In diluted solutions, OH- will give up electrons more readily than other non-
metal ions, and oxygen forms .

Notes Chemistry O.L 2025 76 Dr Peter Alfred

Examples:

Brine (The electrolysis of salt water):

Observation at the cathode: Hydrogen bubbles off (colorless):

Observation at the anode: Chlorine bubbles off (green):

 Na and OH ions are left behind, which means a solution of sodium

+ -

hydroxide forms.

 The products from the electrolysis of brine are:

1. Sodium hydroxide.
2. Chlorine.
3. Hydrogen.

Notes Chemistry O.L 2025 77 Dr Peter Alfred

Very important notes:

These products are used for many purposes:

Sodium hydroxide: is used for making, soaps, detergents and paper.

Chlorine is used for making, PVC, solvents, bleach, drugs, hydrochloric acid ,
paints and dyes.

Hydrogen is used for making fuel for rockets and nylon.

Electrolysis of Dilute Sodium Chloride Solution:

Note: There is a difference in the products between the electrolysis of

dilute sodium chloride solution and concentrated sodium chloride solution.
An aqueous solution of sodium chloride contains four different types of ions.
They are
Ions from sodium chloride – Na+ (aq) and Cl- (aq)
Ions from water – H (aq) and OH (aq)
+ -

When dilute sodium chloride solution is electrolyzed using inert electrodes, the
Na and H ions are attracted to the cathode. The Cl and OH ions are
+ + - -

attracted to the anode.

At the cathode:

The H and Na ions are attracted to the platinum cathode. H ions gains electrons
+ + +

from the cathode to form hydrogen gas. (The hydrogen ions accept electrons more
readily than the sodium ions. As a result, H ions are discharged as hydrogen gas,
+

which bubbles off.

2H+(aq) + 2e H2(g)
Na ions remain in solution.
+

Notes Chemistry O.L 2025 78 Dr Peter Alfred

At the anode:

OH and Cl are attracted to the

- -

platinum anode. OH ions give up

-

electrons to the anode to form

water and oxygen gas.

4OH (aq)
-
2H2O(l) + O2(g) + 4e -

Cl- ions remain in solution.

Summary:
The overall reaction is:

2H2O(l) 2H2(g) + O2(g)

Since water is being removed (by decomposition into hydrogen and

oxygen), the concentration of sodium chloride solution increases
gradually. The overall reaction shows that the electrolysis of dilute
sodium chloride solution is equivalent to the electrolysis of water.
Electrolysis of Dilute sulfuric acid:

Notes Chemistry O.L 2025 79 Dr Peter Alfred

 Electrolysis of Copper (II) sulfate solution (using inert electrodes).

During electrolysis, the cathode is coated with a layer of reddish-brown solid

copper. The blue color of the solution fades gradually as more copper is
deposited. The resulting electrolyte also becomes increasingly acidic.
An aqueous solution of copper (II) sulfate contains four types of ions:

Ions from copper (II) sulfate: Cu2+ and SO4 2-

Ions from water: H+ and OH-

At the anode:
OH- ions and SO4 2- ions are attracted to the anode. OH- ions give up
electrons more readily than SO4 2-
ions. Consequently, OH- ions are
preferentially discharged to give oxygen gas.

4OH (aq)
-
2H2O (l) + O2 (g) + 4e -

The SO 4
2
ions remain in solution.

Notes Chemistry O.L 2025 80 Dr Peter Alfred

At the cathode:
H ions and Cu
+ 2+
ions are attracted to the cathode. Copper is lower than hydrogen in
the reactivity series. Cu 2+
ions accept electrons more readily than H ions. As a
+

result, Cu 2+
ions are preferentially discharged as copper metal (atoms).
Cu 2+
(aq) + 2e Cu (s) The H ions remain in solution.
- +

Summary:

When aqueous copper (II) sulfate is electrolyzed using platinum

electrodes, copper metal is deposited at the cathode and oxygen
gas is given off at the anode.
The overall reaction is:

2CuSO4 (aq) + 2H2O (l) 2Cu (s) + O2 (g) + 2H2SO4(aq)

Summary of electrolysis for molten compounds

1. All ionic compounds when molten can be decomposed when
electricity is passed through using electrolysis.
2. The metal and hydrogen always forms at the cathode.
3. Non-metal always forms at the anode.
4. Cations travel to the cathode.
5. Anions travel to the anode.
6. The electrodes are made from inert material such as graphite, so
that they do not involve themselves with the reaction.
7. The molten substance been electrolyzed is called the electrolyte.

Summary of Aqueous compounds(solution)

Cathode: Anode: N.B. rules: for any aqueous
- least reactive goes - most abundant concentrated compound
to cathode where (available) goes to * cathode: hydrogen
reduction occurs anode where * anode: halogen (non - metal)
(according to oxidation occurs * electrolyte: changed to metal
reactivity series) hydroxide

Notes Chemistry O.L 2025 81 Dr Peter Alfred

Question:
Give the products and the equations of the following:

Conc. NaCl (sodium chloride) Conc. KBr (potassium bromide)

Cathode: -ve Anode: +ve Cathode: Anode:
Hydrogen Chlorine Hydrogen Bromine

Eq: Eq: Eq: Eq:

2H + 2e
+ -
H2 2Cl -
Cl2 + 2e - 2H +2e
+ -
H2 2Br -
Br2 + 2e -

Electrolyte: changed to sodium hydroxide Electrolyte: changed to potassium hydroxide

Conc. HCl (hydrochloric acid) dil. NaCl (sodium chloride)

Cathode: Anode: Cathode: -ve Anode: +ve

Hydrogen Chlorine Hydrogen Oxygen
Eq: Eq:
Eq: Eq:
2H+ + 2e- H2 2Cl- Cl2 + 2e-
2H + 2e
+ -
H2 4OH- O2+2H2O+4e-
Electrolyte:
changed to concentrated to SodiumChloride

dil. H2SO4 (sulfuric acid) Aqueous copper II sulfate using Inert

electrodes
Cathode: Anode:
Cathode: Anode:
Hydrogen Oxygen
Copper II oxygen
Eq: Eq:
Eq: Eq:
2H+ + 2e- H2 4OH- O2+2H2O+4e-
Cu +2e
2+
Cu 4OH- O2+2H2O+4e-

Electrolyte: changed to concentrated

Electrolyte: changed to sulfuric acid
sulfuric acid

The above examples are exam questions, study well

Notes Chemistry O.L 2025 82 Dr Peter Alfred

Applications of electrolysis (Reading):
A- Depositing and purifying of Copper:
When a solution of copper (II) sulfate is electrolyzed using copper electrodes the following
diagram shows that:

At the cathode:
Copper ions become copper atoms:
The copper atoms deposit themselves on the cathode.

At the anode:
The copper anode dissolves, forming copper ions:

Very important note:

1- This method is used to purify copper in industry. By placing the impure copper at
the anode, pure copper is formed at the cathode, as the copper ions migrate from the
impure copper anode.

2-Mass of copper lost at anode = mass of copper gained at cathode.

Notes Chemistry O.L 2025 83 Dr Peter Alfred

 Copper is deposited at the cathode and is dissolved at the anode. Consequently,
the concentration of copper ions in solution remains constant. This can be used
as a method of purification of copper as only pure copper is deposited at the
cathode.

In this purification an anode made of impure copper is turned to pure copper at

the cathode leaving the impurities behind (zinc ions in the solution and silver sludge)

Observation:

Anode becomes thinner and cathode becomes thicker ( increased in size)

Electrolyte: (remains blue copper II sulfate) No change.

B - Electroplating:

• This is a process where the surface of one metal is coated

with a layer of a different metal
• The anode is made from the pure metal used to coat
• The cathode is the object to be electroplated
• The electrolyte is an aqueous solution of a soluble salt of
the pure metal at the anode

Uses of Electroplating

• Electroplating is done to make metals more resistant to corrosion or

damage, e.g: chromium and nickel plating.
 It is also done to improve the appearance of metals, e.g: silver
plating cutlery

At the anode: Silver dissolves forming silver ions.

At the cathode: Silver ions receive electrons and form a layer of silver
on the vase.

Notes Chemistry O.L 2025 84 Dr Peter Alfred

How metals are extracted?

Notes Chemistry O.L 2025 85 Dr Peter Alfred

 Extraction of Aluminum

The method

 The bauxite (red-brown solid) - aluminum oxide

mixed with impurities (Iron III Oxide) - is
extracted from the earth.
 The extracted aluminum oxide is then treated with
alkali (NaOH), to remove the impurities. This results
in a white solid called aluminum
oxide or alumina.
 The alumina is then transported to
huge tanks. The tanks are lined
with graphite, these acts as the
cathode. Also blocks of graphite
hang in the middle of the tank,
and acts as anodes.
(Alumina melts on 2000 degrees)
 The alumina is then dissolved in
molten cryolite (Na3ALF6) - this
lowers the melting point and increases the conductivity so saves
money/Time.
 Electricity is passed and electrolysis begins. Electrolysis is the decomposition of a
compound using electricity.

When dissolved, the aluminum ions and oxide ions in the alumina can move.

At the cathode:
Here the aluminum ions receive electrons to become atoms again:
Al3+ + 3e- AL

At the anode:
The oxide ions lose electrons to become oxygen molecules, O2:
2O2- O2+ 4e-

Why anode is replaced periodically?

Because carbon reacts with oxygen at high temperature forming carbon monoxide and carbon dioxide.

Notes Chemistry O.L 2025 86 Dr Peter Alfred

Uses of Aluminum:

1- Low density and strength make it ideal for

construction of aircraft, lightweight vehicles, and

ladders.

2- An alloy of aluminum called duralumin is often used

instead of pure aluminum because of its improve
properties.

3- Easy shaping and corrosion resistance make it

a good material for drink cans and roofing
materials.

4- Corrosion resistance and low density leads to its

use for greenhouses and window frames.

5- Good conduction of heat leads to its use for boilers,

cookers and cookware.

6- Good conduction of electricity leads to its use for

overhead power cables hung from pylons
(low density gives it an advantage over copper).

Notes Chemistry O.L 2025 87 Dr Peter Alfred

 Extraction of Iron:

The ore of iron is called hematite. It consists of 60% iron in form of Iron oxide (Fe2O3) with other
impurities such as silicon dioxide (SiO2). This process takes place in a tower called a Blast furnace

Reactions in blast furnace

Stage 1: the coke burns giving off heat

The blast of hot air starts the coke burning. It

reacts with the oxygen in the air, giving carbon
dioxide:

Carbon + Oxygen Carbon dioxide

C (s) O2 (g) CO2

Explanation: It’s a combustion reaction which

means it’s a redox reaction. The
carbon is oxidized to carbon dioxide. The blast of
air provides the oxygen for the reaction.

The reaction is exothermic – it gives off heat,

which helps to heat the furnace.

Stage 2 carbon monoxide is formed

The carbon dioxide reacts with more coke, giving

carbon monoxide:

Carbon + Carbon dioxide Carbon monoxide

C (s) CO2 (g) 2CO (g)

Explanation: In this redox reaction, the carbon dioxide loses oxygen. It is reduced.

Notes Chemistry O.L 2025 88 Dr Peter Alfred

Stage 3 Iron (III) oxide is reduced:

This is where the actual extraction occurs. Carbon monoxide reacts with the iron ore giving liquid iron:

Iron (III) oxide + Carbon monoxide Iron + Carbon dioxide

Fe2O3 (s) 3CO (g) 2Fe (l) 3CO2 (g)

Note that: The iron trickles to the bottom of the furnace.

Explanation: In this redox reaction, carbon monoxide acts as the reducing agent. It reduces the iron
(III) oxide to the metal.

At the same time the carbon monoxide is oxidized to carbon dioxide.

Stage 4:

CaCO3 CaO + CO2

Q: What is the role of limestone?

The limestone reacts with the sand (silica) in the ore, to form calcium silicate or slag.

Stage 5:

Lime + Silica Calcium silicate

CaO (s) SiO2 CaSiO3 (s)

The slag runs down the furnace and floats on the iron.

Explanation: The purpose of this reaction is to remove impurities from the molten iron.

Silica is an acidic oxide. Its reaction with limestone is neutralization (because

limestone is a base), giving calcium silicate, a salt.

Notes Chemistry O.L 2025 89 Dr Peter Alfred

Waste gases:

These are carbon dioxide and nitrogen. They come out at the top of the furnace.

Explanation: The carbon dioxide is from the reduction reaction in stage 3. The nitrogen is from the
air blast. It has not taken part in the reactions so has not been changed.

The molten iron is tapped from the bottom. It is impure with carbon as the main impurity. Some is
run into molds to give cast iron. This is hard but brittle (5% carbon, sulfur, silicon and phosphorous).
But most of the iron is turned into steel.

Making steel (by oxygen converter) Reading:

 This is how steels are made:

Unwanted impurities are removed:

1- A beam of oxygen Is Blown onto the

surface of the molten iron Impurities start
to react.
2- Carbon is oxidized into carbon monoxide

and carbon dioxide and escape Sulfur is

oxidized into sulfur dioxide and escapes

3- Silicon and phosphorus are oxidized into

silicon oxide and phosphorus pentoxide
which are solids.

4- Calcium oxide (lime) is added to remove the solid impurities as slag

which is skimmed off the surface

5- Throughout the process, sample of the iron are being taken and analyzed for
the percentage of carbon present in it. When the percentage of carbon desired is
reached, the furnace is switched off and the steel is collected.

Notes Chemistry O.L 2025 90 Dr Peter Alfred

 State the raw materials of extraction of iron:

1- Ore (hematite)
2- Coke carbon
3- Limestone (calcium carbonate)
4- Warm air source of oxygen
5- Water coolant

Write the equations for the extraction of iron:

Equations: “steps”

1- C + O2 CO2 + heat “Exothermic step”

2- CO2 + C 2CO “Reducing agent”

3- Fe2O3 + 3CO 2Fe + 3CO2 “Redox occurs”

4- CaCO3 CaO + CO2 “Thermal decomposition”

5- CaO + SiO2 CaSiO3 “Neutralization”

(Give a brief account on the Conversion of pig iron into steel:(Reading

1- A beam of oxygen is blown into pig iron, (S & C ) reacts with oxygen
to form SO2 / CO2 (waste gases)
2- While silicon & phosphorus forms silicon oxide & phosphorous
oxide that neutralized by calcium oxide to form slag that can be
skimmed.

Notes Chemistry O.L 2025 91 Dr Peter Alfred

 Alloys
An alloy:

Is a mixture of metals that changes their properties or increase them. Turing

a metal into an alloy increases its range of uses.

 Alloys formed by mixing molten metals together then

cooled

Example of alloys: Brass alloy (copper and zinc), bronze (copper

and tin) Pure iron is too soft and stretches easily and rusts.

When carbon (0.5%) is mixed with it, the result is mild

steel. This is hard and strong. When nickel and chromium
are mixed with iron, the result is stainless steel. This is
hard and rustproof.

B-Then other elements added

 Pure metal is formed from

many layers of the same
particle size.
 While Alloys are formed when
pressure is applied and
another metal (or metals) of
different particle sizes are
inserted, layers don’t move
so, alloys are stronger than
pure metals.

Notes Chemistry O.L 2025 92 Dr Peter Alfred

 Commonly used alloys

VIP note:

1- Steel hardness depends on the carbon percentage.

2- The only non-metal element in the alloys is carbon.

Notes Chemistry O.L 2025 93 Dr Peter Alfred