The Electrolysis of Aqueous Solutions

The Electrolysis of
Aqueous Solutions
The electrolysis of aqueous solutions
Aqueous solutions are solutions in water.
Water is a very weak electrolyte. It ionises very slightly

to give hydrogen ions and hydroxide ions.
H2O(l) H+(aq) + OH-(aq)
Solutions, therefore, always contain H+ and OH- ions.
Whenever you have water present, you have to

consider these ions as well as the ions in the
compound you are electrolysing.
Preferential Discharge of Ions
In the electrolysis of compounds which contain more
than one type of anion or cation, one type of ion will
be discharged in preference to the other. This is
known as preferential discharge of ions.
Factors which influence the preferential
discharge of ions
1. The position of the ion in the electrochemical
series.
The ions that are lower in the electrochemical series

get discharged in preference to the ones above them.
This is true for both the cations and the anions.
Example: If a solution contains Cu2+ ions these will be

discharged in preference to H+ ions. But if a solution
contains Na+, the H+ ions will be discharged in
preference to the Na+ ions.
2. The concentration of the aqueous solution.
The concentration of the solution has an impact on

which ions are preferentially discharged.
There is a tendency to promote the discharge of the

most concentrated ion present.
This rule of concentration really only applies when

comparing the anions, especially in solutions
containing halide ions (Cl-, Br-, I-) and does not
usually apply to the cations.
3. The nature of the electrodes: active and inert
electrodes.
The type of electrodes chosen for the electrolysis also

affects the reactions occurring at the electrodes,
especially the anode.
Inert and active electrodes can be distinguished by the

fact that inert electrodes do not take part in the
chemical reaction whereas active electrodes do.
An example of an active electrode is copper, whereas

graphite and platinum are examples of inert
electrodes.
The electrolysis of concentrated
sodium chloride solution
At the cathode:
The solution contains Na+(aq) and H+(aq) and these are

both attracted to the negative cathode.
The H+(aq) gets discharged because it is much easier

to persuade a hydrogen ion to accept an electron
than it is a sodium ion.
Each hydrogen atom formed combines with another

one to make a hydrogen molecule.
2H+(aq) + 2e- ® H2(g)

At the anode:
Cl-(aq) and OH-(aq) are both attracted by the positive

anode.
The hydroxide ion is slightly easier to discharge than

the chloride ion is, but there isn't that much difference.
There are far, far more chloride ions present in the

solution, and so it is mainly these which get
discharged.
2Cl-(aq) ® Cl2(g) + 2e-

The electrolysis of dilute
sodium chloride solution
In a dilute solution there are fewer chloride ions and a
different product is made.
Water ionises a little to give both hydrogen ions (H+)

and hydroxide ions (OH-).
In a dilute solution it is the hydroxide ions that are

discharged at the anode.
Hydroxide ions turn into water and oxygen gas. At the

anode (+) oxygen gas bubbles off.
Position of ions in the electrochemical series
The position of an ion in the series tells us what the
likely products of electrolysis will be.
Carbonate ion These ions are not discharged,

Nitrate ion we get oxygen instead.
Sulphate ion
Hydroxide ion from Halogens are discharged

the water (when concentrated) and
Chloride halide ions stay in solution.
Bromide
Iodide
Summary of the electrolysis of solutions
using carbon electrodes
• If the metal is high in the Reactivity Series,
hydrogen is produced instead of the metal.
• If the metal is below hydrogen in the Reactivity

Series, the metal is produced.
• If you have reasonably concentrated solutions of

halides (chlorides, bromides of iodides) the
halogen (chlorine, bromine or iodine) is produced.
With other common negative ions, oxygen is
produced.
Special Cases
Example: If you have a moderately reactive metal
like zinc.
Reasonably concentrated solutions will give you the

metal.
Very dilute solutions will give you mainly hydrogen.
In between, you will get both.

The electrolysis of some other solutions
KI(aq)
Cathode Equation:
2H+(aq) + 2e- ® H2(g)
Anode Equation:
2I- (aq) ® I2(aq) + 2e-
MgBr2(aq)
Cathode Equation:
2H+(aq) + 2e- ® H2(g)
Anode Equation:
2Br- (aq) ® Br2(aq) + 2e-
H2SO4(aq)
Cathode Equation:
2H+(aq) + 2e- ® H2(g)
Anode Equation:
4OH- (aq) ® 2H2O(l) + O2(g) + 4e-
CuSO4(aq)
Cathode Equation:
Cu2+(aq) + 2e- ® Cu(s)
Anode Equation:
4OH- (aq) ® 2H2O(l) + O2(g) + 4e-
HCl(aq) (concentrated)
Cathode Equation:
2H+(aq) + 2e- ® H2(g)
Anode Equation:
2Cl- (aq) ® Cl2(aq) + 2e-
Active Electrodes
If you use metal electrodes rather than carbon,
different things can happen at the anode, unless the
metal is extremely unreactive – like platinum.
Positive ions are turned into atoms by taking electrons

from the cathode. Electrons are pumped around the
circuit from the anode to replace them. The reactions
at the anode act as a source of these electrons.
So far, these electrons have come from negative ions

giving up electrons to the anode, but there is another
possibility. They can come from atoms in the electrode
itself if that is an easier process.
The electrolysis of copper(II) sulphate
solution using copper electrodes
A copper atom breaks away from the electrode
forming a copper(II) ion, leaving its electrons behind
on the electrode.
Those electrons can then be pumped away by the

power source around the circuit to the cathode.
Cu(s) ® Cu2+(aq) + 2e-

For every copper(II) ion that breaks away from the
anode, two electrons are made available to pump
around the circuit.
That’s exactly what you need to discharge a

copper(II) ion arriving at the cathode.
Cu2+(aq) + 2e- ® Cu(s)

The overall effect is that:
• the anode loses mass
• the cathode gains exactly the same mass
• the number of copper(II) ions in solution doesn’t

change at all. For every one that is discharged at
the cathode, another one goes into solution at the
anode.
Electroplating
Electroplating
Electroplating consists of depositing a thin layer of
one metal on top of another, either to protect the inner
layer or for the sake of appearance.
The object which is being electroplated can be made

of any metal, but most often it is made of brass, nickel
or steel.
Example 1 – Silver Plating
Electroplating A Spoon with Silver
Example 2 – Nickel Plating
Electroplating A Nail with Nickel
Electroplating Procedure
• The object to be electroplated is made the cathode, i.e.
it is connected to the negative terminal of the battery.
• The anode is usually a pure sample of the metal which is

being used for plating. The anode is therefore active and
ionises.
• The electrolyte must contain ions of the metal which is

being used for plating.
Examples of electroplating are chromium plating, silver

plating and nickel plating.
Example 3 -Chromium Plating
Chromium Plating
Chromium plating makes use of a steel cathode and a
pure chromium anode.
The electrolyte is a mixture of chromium(III) sulphate and

a wetting agent.
The wetting agent facilitates optimal bonding of the

chromium to the steel object, preventing the chromium
layer from flaking off easily.
Chromium plating improves the look and strength of the

steel object as well as protecting the steel layer from
corrosion.
Chromium Plating
The reaction at the anode is:
Cr(s) ® Cr3+(aq) + 3e-
The reaction at the cathode is:

Cr3+(aq) + 3e- ® Cr(s)

The Electrolysis of Aqueous Solutions

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The Electrolysis of Aqueous Solutions

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The Electrolysis of

Water is a very weak electrolyte. It ionises very slightly

H2O(l) H+(aq) + OH-(aq)

Solutions, therefore, always contain H+ and OH- ions.

Whenever you have water present, you have to

The ions that are lower in the electrochemical series

Example: If a solution contains Cu2+ ions these will be

The concentration of the solution has an impact on

There is a tendency to promote the discharge of the

This rule of concentration really only applies when

The type of electrodes chosen for the electrolysis also

Inert and active electrodes can be distinguished by the

An example of an active electrode is copper, whereas

The solution contains Na+(aq) and H+(aq) and these are

The H+(aq) gets discharged because it is much easier

Each hydrogen atom formed combines with another

2H+(aq) + 2e- ® H2(g)

Cl-(aq) and OH-(aq) are both attracted by the positive

The hydroxide ion is slightly easier to discharge than

There are far, far more chloride ions present in the

2Cl-(aq) ® Cl2(g) + 2e-

Water ionises a little to give both hydrogen ions (H+)

In a dilute solution it is the hydroxide ions that are

Hydroxide ions turn into water and oxygen gas. At the

Carbonate ion These ions are not discharged,

Hydroxide ion from Halogens are discharged

• If the metal is below hydrogen in the Reactivity

• If you have reasonably concentrated solutions of

Reasonably concentrated solutions will give you the

Very dilute solutions will give you mainly hydrogen.

In between, you will get both.

Positive ions are turned into atoms by taking electrons

So far, these electrons have come from negative ions

Those electrons can then be pumped away by the

Cu(s) ® Cu2+(aq) + 2e-

That’s exactly what you need to discharge a

Cu2+(aq) + 2e- ® Cu(s)

• the anode loses mass

• the cathode gains exactly the same mass

• the number of copper(II) ions in solution doesn’t

The object which is being electroplated can be made

• The anode is usually a pure sample of the metal which is

• The electrolyte must contain ions of the metal which is

Examples of electroplating are chromium plating, silver

The electrolyte is a mixture of chromium(III) sulphate and

The wetting agent facilitates optimal bonding of the

Chromium plating improves the look and strength of the

The reaction at the cathode is:

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