Electrolysis

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Electrolysis of aqueous solutions
When a solute M+A– is in an aqueous solution, there is
more than one redox reaction possible at each
electrode.

• at the anode: either A– or H2O can be oxidized;

• at the cathode: either M+ or H2O can be reduced.

The discharge of an ion at the electrode in these cases

is known as selective discharge.

The outcome is determined by the following factors:

a) The relative E˚ of the ions
b) The relative concentrations of the ions in the
electrolyte
c) The nature of the electrode
a) The relative E˚ of the ions

• Species with higher reduction potential( less

negative) will reduce at cathode

• Species with higher oxidation potential will

oxidize at anode
 Electrolysis of water
The ionization of pure water is very low.
However, the addition of ions increases its conductivity so some
compound like H2SO4 , NaOH is added when electrolysis is
performed.
Electrolysis of water (containing NaOH)
Electrolysis of water
3. Observations:
Cathode: Bubbles of colorless gas (H2).
H2O(l) + e →½H2(g)+OH–(aq) pH increases as H+ is discharged
(consumed).
Anode: Bubbles of colorless gas (O2). pH
2OH–(aq) → ½O2(g) + H2O(l) decreases as OH- is discharged.
+ 2e–
Electrolyte: Ratio of volumes of O2:H2 is 1:2
2H2O(l) → O2 (g) + 2H2(g)

Discharged = removal of the charges on the ions and

forming neutral products.
 Electrolysis of Dilute NaCl(aq)
The electrolysis of dilute NaCl(aq) leads to the production of H2
and O2.
Ions present: NaCl(aq) → Na+ + Cl-
 Electrolysis of Dilute NaCl(aq)
Observations:
Cathode: Bubbles of colorless gas (H2).
H2O(l) +e→½H2(g)+OH–(aq) pH increases as H+ is discharged
(consumed).
Anode: Bubbles of pale green gas (Cl2).
2Cl–(aq) → Cl2(g) + 2e– Cl2(g) identified through strong
smell and bleaching effect on
damp blue litmus paper.
Electrolyte: Increase in pH of the electrolyte
2Cl–(aq) + 2H2O(l) → Cl2(g) will occur due to formation of OH–.
+ H2(g) + 2OH–(aq)
 ELECTROLYSIS OF CuSO4(aq)
• CuSO4(aq) is bright blue due to the
hydrated Cu2+ ion.
• Electrolysis of this solution yields
different products depending on the
nature of the electrodes.
- Inert platinum or graphite (carbon)
electrodes
- Active copper electrodes
 ELECTROLYSIS OF CuSO4(aq)
3. Observations
Cathode: Pink brown colour of copper
Cu2+(aq) + 2e– → Cu(s) deposited on cathode.

Anode: Bubbles of colorless gas (O2).

H2O(l) → ½O2(g) + 2H+(aq) +
2e–
Electrolyte: Decrease in pH of the solution
2Cu2+(aq) + 2H2O(l) → due to increase in concentration
2Cu(s) + O2(g) + 4H+(aq) of H+.
Loss of intensity of blue colour
due to discharge of Cu2+.
b) The relative concentrations of the ions in
the electrolyte
When two ions with similar reactivity are in competition
then the relative concentration of the two ions
becomes an important factor.

A good example of this is the electrolysis of sodium

chlorides (Brine).

When the chloride concentration is large the chloride

ions lose electrons and chlorine gas is released at the
electrode, but when it is in low concentration then
water is preferentially discharged to release oxygen
gas
Electrolysis of concentrated NaCl(aq) (Brine)
1. Ions present
Electrolysis of concentrated NaCl(aq) (Brine)
• 3. The overall equation when Cl- is discharged:
2NaCl(aq) + 2H2O(l) → 2H2(g) + Cl2(g) + 2Na+ + 2OH-

• 4. The observed changes at electrodes:

– A gas evolves at both electrodes –
• Cl2 at anode and H2 at cathode

– Cl2(g) is identified at the anode through its strong

smell and bleaching effect on blue litmus paper.

https://www.youtube.com/watch?v=1FDzt5VP50c
 c) The nature of the electrode
The nature of electrode used also effect the product
formed during electrolysis

Consider the electrolysis of copper sulfate solution using

two different sets of electrodes.
1. using graphite electrodes

2. using copper electrodes

• 3. So the net reaction
is the movement of
Cu2+ from where it is
produced at the anode
to the cathode where
it is discharged as
Cu(s).

. The observed changes at electrodes:

– Pinky-brown color develops as copper is deposited
on the cathode.
– Disintegration of the Cu anode.
– No change in pH.
– No change in intensity of blue color as the
concentration of Cu2+ remains constant.
Factors affecting the amount of
product in electrolysis
• The three factors influencing the amount of
products are:
– The charge on the ion
– The current
– The duration of the electrolysis
• There are two types of problems involving
electrolysis.
– Solve for amount of product.
– Solve for time.
 Charge = current x time
• Q=It
Q = Charge measured in coulomb (C),
I = current measured in amperes (A)
t= time measured in seconds (s).
• The charge carried by one mole of electrons, known as a
Faraday (F), is 96 500 C.
Q1 How many grams of copper are deposited on the cathode
of an electrolytic cell containing CuCl2(aq) if a current of 2.00
A is run for 15.0 minutes?

Q = current x time = 2.00 A x (15.0 x 60s) = 1800 C

F = Q ÷ 96500 = 1800 C ÷ 96500 = 0.01865 mol of e–

Use mole ratio in the electrode half-equation:

Cu2+(aq) + 2e– → 1Cu(s)
2 mol e– : 1 mol Cu
0.01865 mol e– : ??
Moles of product (Cu) = 0.01865 ÷ 2 = 0.00933 mol Cu
Mass of product = moles x molar mass
= 0.00933 x 63.55 = 0.593 g Cu
(b) How would the amount differ if the same conditions were
applied using CuCl(aq) instead?

The equation for discharge from CuCl(aq) is

Cu+(aq) + e– → 1Cu(s)
1 mol e– : 1 mol Cu
0.01865 mol e– : ??

Moles of product (Cu) = 0.01865 mol Cu

Mass of product = moles x molar mass
= 0.01865 x 63.55 = 1.19 g Cu
Q If a current of 2.00 A is passed through a solution of
AgNO3 for 10 minutes, 0.0124 moles of Ag are formed.
(a) How much Ag moles would form if a current of 1.00 A
is passed through the same solution for 30 minutes?

Solution
Charge = current x time
Current is reduced by half
Time is increased by 3

So the new charge will be 1.5 times the previous charge

Therefore the amount of product = 0.0124 mol x1.5

= 0.0186 mol Ag
(b) What amount of Cu would form if the quantity of electricity
in (a) was passed through a solution of CuSO4?

Cu2+(aq) + 2e– → Cu(s)

2 mol e– : 1 mol Cu
0.0186 mole e– : ?? mol Cu

Cu = 0.0186 ÷ 2
= 0.0093 mol Cu
 Question
◼ If the same current is passed for the same time through an
aqueous solution containing sodium ions and an aqueous
solution containing lead ions, then which cell will produce
the larger amount of metal at the cathode? Why?

◼ Amount of metal produced at the cathode of the sodium cell

will be twice as large as that produced in the lead cell,
because the reduction of a sodium ion requires only one
mole electron whereas the reduction of a lead ion requires
two mole electrons.
Calculate the volume of hydrogen gas (in cm3) produced
at STP when a current of 4.00 A is passed for 6 minutes
and 10 seconds through a solution containing dilute
aqueous sulfuric acid.

Current (I) = 4.00 A ; Time = 370 s

Charge (Q) = 4. 00 x 370 = 1480 C;
F = Q ÷ 96500 = 1480 C ÷ 96500 = 0.0153 mol of e–
2H2O(l) + 2e- → H2(g) + 2OH-
2 mol e– : 1 mol H2
0.0153 mole e– : ?? mol H2
Therefore moles of H2 = 7.67 x 10-3 mol
volume of H2 = 7.67 x 10-3 mol x 22700 cm3
= 174 cm3
 Question
◼ Which changes lead to the production of more moles of
metal during the electrolysis of a molten salt?
I. using a metal ion with a higher charge
II.increasing the current
III.using a longer time

A.I and II only

B.I and III only
C.II and III only
D.I, II and III
 Question
◼ Which of the following causes the largest amount of
copper to be deposited during electrolysis?

A. Cu(I)Cl 5.00 amps 10 min

B. Cu(II)Cl2 5.00 amps 10 min
C. Cu(I)Cl 2.00 amps 30 min
D. Cu(II)Cl2 2.00 amps 30 min
 ELECTROPLATING
Electroplating is the process of using electrolysis to deposit a
layer of metal on top of another metal or conductive substance

PURPOSES OF ELECTROPLATING

• Decorative purposes
• Corrosion control
• Improvement of function
.
 ELECTROPLATING
For electroplating
• An electrolyte containing the metal ions which are to be
deposited.
• The cathode made of the object to be plated
• The anode must be the same metal which is to be coated.

Process can be controlled

by altering the current and
time according to how
thick a layer of metal is
desired.
 ELECTROPLATING
At the cathode the silver ions undergo reduction to form silver
atoms:
Ag+(aq) + e− − → Ag(s)

At the anode the silver atoms undergo oxidation:

Ag(s) → Ag+(aq) + e−

As the current flows through the circuit, the anode slowly

dissolves and replaces the silver ions in the electrolyte.
 Uses of electroplating
1. Decorative purposes
◼Covering a metal with a layer of a more expensive or
decorative metal, such as silver- and nickel-plating of cutlery.
2. Corrosion control
◼Iron with a layer of zinc deposited on its surface, known as
galvanized iron, is protected from corrosion as the zinc will be
preferentially oxidized. This is sometimes called sacrifcial
protection.
3. Improvement of function
◼Electroplatingwith chromium improves the wear on steel
parts such as crankshafts and hand tools.