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. I will elaborate later.

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 electrolysed 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. I will explain why H+ ions are
preferentially discharged later.)

2H+(aq) + 2e- à H2(g)

Na+ ions remain in solution.

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) à 2H2O(l) + O2(g) + 4e-

Cl- ions remain in solution.

Summary:

The overall reaction is:

2H2O(l) à 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.
Another important thing to note is that twice as much hydrogen is produced as oxygen. This is
because for every 4 electrons that flows around the circuit, you would get one molecule of oxygen.
But four electrons would produce 2 molecules of hydrogen. Hence in a diagram, you would see the
volume of hydrogen produced is twice that of oxygen. Refer to the equations above and note the
number of electrons involved to help you understand.

This diagram is just to illustrate how twice as much hydrogen gas is produced.

Electrolysis of Concentrated Sodium Chloride Solution

The only difference is that at the anode, Cl- ions are more numerous than OH- ions. Consequently, Cl-
ions are discharged as chlorine gas, which bubbles off.

2Cl- (aq) à Cl2(g) + 2e-

The OH- ions remain in solution.

One volume of hydrogen gas is given off at the cathode and one volume of chlorine gas is produced
at the anode. The resulting solution becomes alkaline because there are more OH- than H+ ions left in
the solution.
Comparison:

Compare the electrolysis of molten sodium chloride, dilute sodium chloride solution and
concentrated sodium chloride solution:

Molten sodium chloride:

 Cathode: Na+ ions discharged

 Anode: Cl- discharged

Dilute NaCl solution:

 Cathode: H+ ions discharged

 Anode: OH- discharged

Concentrated NaCl solution:

 Cathode: H+ discharged

 Anode: Cl- discharged

So you can see that Na+ and Cl- ions are not always discharged even though in all 3 of the above, the
electrolytes contained these ions. For example in the electrolysis of dilute NaCl solution, H+ are
discharged in preference to Na+ ions. OH- ions are discharged in preference to Cl- ions. Before I talk
about the electrolysis of copper(II) sulfate and dilute sulfuric acid, I will discuss why one type of
cation (or anion) in the electrolyte is more readily discharged than another type. If you already know
this, just scroll right down. :)
Note: Most of the following is taken from a G.C.E. 'O' Level textbook, but I find it useful. :)

Reactivity Series and Selective Discharge of Ions

In electrolysis, when more than one type of cation or anion is present in a solution, only one cation
and one anion are preferentially discharged. This is known as the selective discharge of ions.

How do you predict which ions are discharged in the electrolysis of a compound in aqueous solution?

If inert electrodes are used during electrolysis, the ions discharged and hence the products formed
depend on three factors:

1. The position of the metal (producing the cation) in the reactivity series.

2. The relative ease of discharge of an anion.

3. The concentration of the anion in the electrolyte.

The ease of discharge of cations and anions during electrolysis is shown below.

Cations Anions

Potassium ion, K+ NB: Ease of discharge increases Chloride ion, Cl-

as you go down the table
Sodium ion, Na+ Bromide ion, Br-

Calcium ion, Ca2+ Iodide ion, I-

Magnesium ion, Mg2+ Hydroxide ion, OH-

Zinc ion, Zn2+

Iron ion, Fe2+ Note: sulphate ions (SO42-) and

nitrate ions (NO3-) will not be
Lead ion, Pb2+ discharged during electrolysis.

Hydrogen ion, H+

Copper ion, Cu2+

Silver ion, Ag+

Selective discharge of cations during electrolysis

The cations of an element lower in the reactivity series are discharged at the cathode in preference
to cations above it in the solution. This is because cations of a less reactive element accept electrons
more readily. For example, if a solution containing Na+ and H+ ions is electrolysed, H+ ions are
discharged in preference to Na+ ions. The more reactive the metal, the more stable its compound.
They have lost a lot of energy and have lost electrons to form stable cations, so cations lower down
the reactivity series are more readily discharged.
Selective discharge of anions during electrolysis
Sulphate (SO42-) and nitrate (NO3-) ions remain in the solution and are not discharged during
electrolysis. If a solution containing SO42-, NO3- and hydroxide (OH-) ions is electrolysed, the OH- ions
will be discharged in preference to SO42- and NO3- ions. The OH- ions give up electrons most readily
during electrolysis to form water and oxygen.

4OH- (aq) à 2H2O (l) + O2 (g) + 4e-

Effect of concentration on selective discharge of anions

An increase in the concentration of an anion tends to promote its discharge. For example, in the
electrolysis of concentrated sodium chloride solution, two types of ions are attracted to the
anode: Cl- and OH- ions. According to their relative ease of discharge, OH- ions should be discharged
preferentially. However, in concentrated sodium chloride solution, Cl- ions are far more numerous
than OH- ions and so are discharged at the anode instead.

2Cl- (aq) à Cl2 (g) + 2e-

What are the general rules for predicting selective discharge?

The following rules can be applied when predicting the products of electrolysis of any aqueous
solution (using inert electrodes):

Rule 1 Identify the cations and anions in the electrolysis. Remember that an aqueous solution
also contains H+ and OH- ions from the dissociation of water molecules.

Rule 2 At the anode, the product of electrolysis is always oxygen unless the electrolyte contains a
high concentration of the anions, Cl-, Br- or I- ions.

Rule 3 At the cathode, reactive metals such as sodium and potassium are never produced during
electrolysis of the aqueous solution. If the cations come from a metal above hydrogen in
the reactivity series, then hydrogen will be liberated (liberate=release). If the cations come
from a metal below hydrogen, then the metal itself will be deposited.

Rule 4 Identify the cations and anions that remain in the solution after electrolysis. They form the
product remaining in solution. Summarise the reactions.

For example, in the electrolysis of dilute sodium chloride solution, Na+ and Cl-ions remain
in solution after H+ and OH- ions have been discharged. Hence the solution of sodium
chloride becomes more concentrated after electrolysis.

Electrolysis of Copper (II) sulphate solution

Copper (II) sulphate solution can be electrolysed using inert platinum electrodes. (Sometimes inert
carbon electrodes in the form of graphite are used.)

During electrolysis, the cathode is coated with a layer of reddish-brown solid copper. The blue colour
of the solution fades gradually as more copper is deposited. The resulting electrolyte also becomes
increasingly acidic.

An aqueous solution of copper (II) sulphate contains four types of ions:

 Ions from copper (II) sulphate: Cu2+ and SO42-

 Ions from water: H+ and OH-

At the anode:
OH- ions and SO42- ions are attracted to the anode. OH- ions give up electrons more readily than SO42-
ions. Consequently, OH- ions are preferentially discharged to give oxygen gas.

4OH- (aq) à 2H2O (l) + O2 (g) + 4e-

The SO42 ions remain in solution.

At the cathode:

H+ ions and Cu2+ ions are attracted to the cathode. Copper is lower than hydrogen in the reactivity
series. Cu2+ ions accept electrons more readily than H+ ions. As a result, Cu2+ ions are preferentially
discharged as copper metal (atoms).

Cu2+ (aq) + 2e- à Cu (s)

The H+ ions remain in solution.

Summary:

When aqueous copper (II) sulphate is electrolysed 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) à 2Cu (s) + O2 (g) + 2H2SO4 (aq)

Electrolysis of dilute sulfuric acid solution
Inert carbon or platinum electrodes are used.
At the cathode:
In this case, the only positive ions arrive at the cathode are the hydrogen ions from the acid and the
water. (Adding acid to water forces it to split up/hydrolyse.) These are discharged to give hydrogen
gas.

2H+ (aq) + 2e- à H2 (g)

At the anode:

At the anode, SO42- ions and OH- ions (from the water) accumulate. OH- ions are discharged to
give O2 gas.

4OH- (aq) à 2H2O (l) + O2 (g) + 4e-

The amount of hydrogen produced is twice that of oxygen. Just like in the electrolysis of dilute
sodium chloride solution. For every 4 e- that flows around the circuit, you would get one molecule
of O2 . But four electrons would produce 2 molecules of H2.