ELECTROLYTIC CELLS

Electrolysis

-uses an external power source to

cause a non-spontaneous reaction to
occur
ÒXIDATION REDUCTION
 Three Main Types of
Electrolytic Cells
1. Electrolysis of Molten Salts (no H2O)
with Unreactive (Inert) Electrodes
2. Electrolysis of Aqueous Salts
(H2O solution)
with Unreactive (Inert) Electrodes
3. Electrolysis of Aqueous Salts (H2O solution)
with Reactive Electrodes
TYPE I: Electrolysis of Molten Salts (no H2O)
with Unreactive (Inert) Electrodes
Inert
Carbon
Electrodes

Molten
ZnCl2
 Electrolysis of Molten Salts (no H2O)
with Unreactive (Inert) Electrodes

O: 2 Cl- → Cl2(g) + 2e- Eoox = -1.359 V

R: Zn2+ + 2e- → Zn(s) Eored = -0.763 V

Zn+ + 2 Cl- → 2 Zn(s) + Cl2(g) Eo = -2.122 V

Product at the cathode: Zn(s)
Product at the anode: Cl2(g)
Electrolysis of Molten Salts (no H2O)
with Unreactive (Inert) Electrodes
Example:
For the Electrolysis of molten sodium chloride
(NaCl),
O: 2 Cl- → Cl2(g) + 2e- Eoox = -1.359 V
R: 2 (Na+ + e- → Na(s)) Eored = -2.71 V

2 Na+ + 2 Cl- → 2 Na(s) + Cl2(g) Eo = -4.069 V

Product at the cathode: Na(s)
Product at the anode: Cl2(g)
 APPLICATION
Production of SODIUM METAL through
Electrolysis of molten NaCl
• It is commercially carried out in cells called Downs cells at
around 600°C.
• The anode and cathode chambers are separated by a
steel screen to prevent contact between molten sodium
metal and chlorine gas to prevent an explosive reaction
between the two reactive elements.
• The molten sodium metal forms a layer above the molten
NaCl and can be siphoned off.
Example:
For the Electrolysis of molten Potassium
Iodide (KI),
O: 2 I- → I2(g) + 2e- Eo = -0.534 V
R: 2(K+ + e- → K(s)) Eo = -2.936 V

2 K+ + 2 I- → 2 K(s) + I2(g) Eo = -3.470 V

Product at the cathode: K(s)
Product at the anode: I2(g)
 TYPE II: Electrolysis of Aqueous Salts
(H2O solution) with Unreactive (Inert) Electrodes

Water could be
oxidized

Water could be
reduced
 Electrolysis of water

• At the anode, hydroxide ions give up e-

to form oxygen gas
• At the cathode, hydrogen ions combine
with e- to form hydrogen gas
Electrolysis of water
 TYPE II: Electrolysis of Aqueous Salts
(H2O solution) with Unreactive (Inert) Electrodes

Since water can also be electrolyzed, the following

could occur at the cathode of a cell with aqueous
salts:
• The reduction of a cation to a corresponding
metal.
• The reduction of a water molecule to hydrogen
gas.
 TYPE II: Electrolysis of Aqueous Salts
(H2O solution) with Unreactive (Inert) Electrodes

And at the anode,

• The oxidation of an anion to the corresponding
nonmetal
• The oxidation of a water molecule to oxygen
gas
Example:
Electrolysis of aqueous copper (II) chloride (CuCl2)
Example:
Electrolysis of aqueous copper (II) chloride (CuCl2)

Possible reduction reactions

R: Cu2+ + 2e- → Cu(s) Eored = 0.337 V
or
R: 2H2O + 2e- → H2(g) + 2OH-(aq) Eored = -0.83 V

Copper will undergo reduction since it will need lesser

voltage for the reaction to occur.
Example:
Electrolysis of aqueous copper (II) chloride (CuCl2)
Possible oxidation reactions
O: 2Cl- → Cl2(g) + 2e- Eoox = -1.359 V
or
O: 2H2O → 4H+(aq) + O2(g) + 4e- Eoox= -1.23 V

Ideally, water will undergo oxidation since it will need lesser voltage for
the reaction to occur.
In actual electrolysis, Cl2 is formed at the anode instead of O2. This is
because the formation of O2 involves higher activation energy
(overvoltage), thus kinetically less favorable.
Activation energy
- the minimum amount of energy that is required to activate
atoms or molecules to a condition in which they can
undergo chemical transformation or physical transport

Overpotential or overvoltage
- directly related to a cell's voltage efficiency
- the extra energy is lost as heat
- can be over 0.5 V if a gas is produced
Example:
Electrolysis of aqueous copper (II) chloride (CuCl2)
O: 2Cl- → Cl2(g) + 2e- Eoox = -1.359 V
R: Cu2+ + 2e- → Cu(s) Eored = 0.337 V

2Cl- + Cu2+ → Cl2(g) + Cu(s) Eo = -1.022 V

Product at the cathode: Cu(s)

Product at the anode: Cl2(g)
TYPE III: Electrolysis of Aqueous Salts (H2O solution)
with Reactive Electrodes
Example:
Electrolysis of aqueous nickel sulfate (NiSO4)

Possible oxidation reactions

O: 2SO42-(aq) → S2O82-(aq) + 2e- Eoox = -2.01 V
O: Ni (s) → Ni2+(aq) + 2e- Eoox = 0.28 V
O: 2H2O → 4H+(aq) + O2(g) + 4e- Eoox= -1.23 V

Nickel will undergo oxidation since it will need lesser voltage

for the reaction to occur.
Example:
Electrolysis of aqueous nickel sulfate (NiSO4)

Possible reduction reactions

R: Ni2+(aq) + 2e- → Ni(s) Eored = -0.28 V
or
R: 2H2O + 2e- → H2(g) + 2OH-(aq) Eored = -0.83 V

Nickel ions will undergo reduction since it will need lesser

voltage for the reaction to occur.
Example:
Electrolysis of aqueous nickel sulfate (NiSO4)
Example:
Electrolysis of aqueous nickel sulfate (NiSO4)
 APPLICATION
Electroplating

Electroplating is the coating of one metal on the surface by

means of electrolysis.

The object to be plated serves as the cathode and the plating

metal serves as the anode.

The metals which are most commonly used in electroplating

include gold, silver, copper, nickel and chromium.
 APPLICATION
Electroplating

The thin coating protects metals from corrosion, serves as

decoration, help in conduction of electricity, reduce friction
and even protect from radiation.

Plating a thin coating of a metal that resists corrosion can

protect other metals that readily corrode.

The electrolyte used usually contains a low concentration of

electroplating metal.
 APPLICATION
Electrorefining

Electrorefining is the purification of metals from their ores or

compounds by means of electrolysis.
 APPLICATION
Electrorefining
 Quantitative Relationships
In an electrolytic cell, there is a simple relationship between the
amount of electricity passed through it and the amount of
substances produced by oxidation or reduction at the electrodes.
According to Michael Faraday’s Law of Electrolysis,
“The amount of electrical charge introduced to the
nonspontaneous system is proportional to the chemical change
produced and that a quantity of electricity produces a
corresponding amount of substance being electrolyzed.”
Quantitative Relationships
 Quantitative Relationships
1. Number of moles of electrons, n
From the balanced half-reactions,
Ag+(aq) + e- → Ag(s)
Cu2+(aq) + 2e- → Cu(s)
it can be deduced that
1 mol of e- → 1 mol of Ag (107.9 g)
2 mol of e- → 1 mol of Cu (63.55 g)
 Quantitative Relationships
(Electrical Units)

2. Quantity of electrical charge

The common unit is coulomb, C, the charge carried by a
mole of electrons through the Faraday constant.
1 mol e- = 96, 480 C
1 Farad = 96,480 C/mol of e-
 Quantitative Relationships
(Electrical Units)

3. Rate of current flow

I = q/t
The common unit is ampere, A. When a current of one
ampere passes through an electrical circuit, one coulomb
passes a given point in the circuit in one second.
1 A = 1 C/s
 Quantitative Relationships
(Electrical Units)
4. Amount of electrical energy
E= qV
This can be expressed in joules, J. When a charge of
one coulomb moves through a potential difference of
one volt, it acquires an energy of one joule.
1 J = 1 C·V
Another unit is the kilowatt hour which is used in our
electric bills.
1 kWh = 3.6 x 106 J
Quantitative Relationships
(Electrical Units)
 Sample Problem
Chromium metal can be electroplated from a water solution
of potassium dichromate, reduction half-reaction is
Cr2O7-(aq) + 14H+(aq) + 12e- → 2Cr(s) + 7H2O
a. How many grams of chromium will be plated by 1 x 104 C?
b. How long will it take to plate one gram of chromium using
a current of 6 A?
c. If the applied voltage is 4.5 V, how many kilowatt hours of
electrical energy are required to plate 1 of Cr?
Practice
1. In an electrolysis of a solution containing
Ni2+ (aq), metallic Ni(s) deposits on the cathode.
Using a current of 0.150 A for 12.2 minutes,
what mass of nickel will form?
Practice
2. Metallic magnesium can be made by the
electrolysis of molten MgCl2.
a. What mass of Mg is formed by passing a
current of 5.25 A through molten MgCl2 for
2.5 days?
b. How many minutes are needed to plate out
10 g of Mg from molten MgCl2 using 3.5 A
current?
Activity
1. In a copper plating experiment in which
copper metal is deposited from copper (II) ion
solution, the system is run for 2.6 hours at a
current of 12 A. What mass of copper is
deposited?
Activity
2. A lead storage battery delivers a current of 6
A for one hour and 22 minutes at a voltage of
12 V.
a. How many grams of lead are converted to
PbSO4?
b. How much electrical energy is produced in
kilowatt hours?
Activity
3. An electrolytic cell with molten Al2O3 produces ten
kilograms (of the product at the cathode) a day.
a. Draw the electrolytic cell and label the electrodes
with the corresponding products.
b. How many electrons must pass through the cell in
one day?
c. How many amperes are passing through the cell in
one day?
d. How many moles of the product at the anode are
being produced?