Electrolysis

- Electrolytic cells
- Quantitative aspects of electrolysis

Electrolysis
Electrolysis is the passage of a direct current through an ionic
substance that is either molten or dissolved in a suitable solvent,
resulting in chemical reactions at the electrodes and separation of
materials.

The main components required to achieve electrolysis are :
An electrolyte : a substance containing free ions which are the carriers
of electric current in the electrolyte. If the ions are not mobile, as in a
solid salt then electrolysis cannot occur.

Electrodes of metal, graphite and semiconductor material are widely
used. Choice of suitable electrode depends on chemical reactivity
between the electrode and electrolyte and the cost of manufacture.

Process of electrolysis

An electrical potential is applied across a pair of electrodes
immersed in the electrolyte.
Each electrode attracts ions that are of the opposite charge.
Positively charged ions (cations) move towards the
electron-providing (negative) cathode, whereas
negatively charged ions (anions) move towards the
positive anode.

At the electrodes, electrons are absorbed or released by the
atoms and ions. Those atoms that gain or lose electrons to
become charged ions pass into the electrolyte. Those ions
that gain or lose electrons to become uncharged atoms
separate from the electrolyte.

Oxidation and reduction at the electrodes

Oxidation of ions or neutral molecules occurs at the anode,
and the reduction of ions or neutral molecules occurs at
the cathode. For example, it is possible to oxidize ferrous
ions to ferric ions at the anode:
Fe
2+
(aq) Fe
3+
aq + e

Electrolysis reactions involving H
+
ions are fairly common in
acidic solutions. In alkaline water solutions, reactions
involving OH
-
(hydroxide ions) are common.
The substances oxidised or reduced can also be the solvent
(usually water) or the electrodes. It is possible to have
electrolysis involving gases.
The Electrolysis of Molten NaCl

An idealized cell for the electrolysis of sodium chloride is shown in the
figure below. A source of direct current is connected to a pair of inert
electrodes immersed in molten sodium chloride. Because the salt has
been heated until it melts, the Na
+
ions flow toward the negative
electrode and the Cl
-
ions flow toward the positive electrode.

When Na
+
ions collide with the negative electrode, the battery carries a
large enough potential to force these ions to pick up electrons to form
sodium metal.
Electrolysis of NaCl:

Negative electrode (cathode):
Na
+
+ e- Na

Positive electrode (anode):
2 Cl
-
Cl
2
+ 2 e-

The net effect of passing an electric current through the molten salt in
this cell is to decompose sodium chloride into its elements, sodium metal
and chlorine gas.

The potential required to oxidize Cl
-
ions to Cl
2
is -1.36 volts and the
potential needed to reduce Na
+
ions to sodium metal is -2.71 volts.

The battery used to drive this reaction must therefore have a potential of
at least 4.07 volts.
The Electrolysis of Aqueous NaCl

Cathode (-):
Na
+
+ e- Na E
o
red = -2.71 V
2H
2
O + 2 e- H
2
+ 2OH
-
E
o
red = -0.83 V

Because it is much easier to reduce water than Na+ ions, the only product
formed at the cathode is hydrogen gas.

Cathode (-): 2 H
2
O(l) + 2 e- H
2
(g) + 2 OH
-
(aq)

Anode (+): 2 Cl
-
Cl
2
+ 2 e- E
o
ox = -1.36 V
2 H
2
O O
2
+ 4H
+
+ 4 e- E
o
ox = -1.23 V

The standard-state potentials for these half-reactions are so close to each
other that we might expect to see a mixture of Cl
2
and O
2
gas collect at the
anode. In practice, the only product of this reaction is Cl
2
.
Anode (+): 2 Cl
-
Cl
2
+ 2 e-

Exercise:
1. Write a net ionic equation for the expected reaction when the
electrolysis of NiSO
4
(aq) is conducted using
(a) a nickel anode and an iron cathode
(b) a nickel anode and an inert platinum cathode
(c) an inert platinum anode and a nickel cathode

2. Use electrode potential data to predict the probable products and
the minimum voltage required in the elctrolysis with inert electrodes
of each of the following:
(a) ZnSO
4
(aq) (b) MgBr
2
(l) (c) NaNO
3
(aq)
Electrolysis of Water
A standard apparatus for the electrolysis of water is shown in the
figure below.
2 H
2
O + 2 e- H
2
+ 2OH
-
E
o
red = -0.83 V
2 H
2
O O
2
+ 4H
+
+ 4 e- E
o
ox = -1.23 V

Faraday's Law of Electrolysis
The amount of a substance consumed or produced at one of the
electrodes in an electrolytic cell is directly proportional to the
amount of electricity that passes through the cell.

By definition, one coulomb of charge is transferred when a 1-amp
current flows for 1 second.
1 C = 1 amp
-s

Example: To illustrate how Faraday's law can be used
Calculate the number of grams of sodium metal that will form at the
cathode when a 10.0-amp current is passed through molten sodium
chloride for a period of 4.00 hours.
We start by calculating the amount of electric charge that flows
through the cell.
Amount of charges = 10.0A x (4x3600s)
= 144 000C
Faraday's constant = 96 484.56 C/mol

Thus, the number of moles of electrons transferred when 144,000
coulombs of electric charge flow through the cell
= 144 000/96484.56 mol
= 1.49 mole of electrons

According to the balanced equation for the reaction that occurs at the
cathode of this cell, we get one mole of sodium for every mole of
electrons.
Cathode (-): Na
+
+ e- Na

Thus, we get 1.49 moles, or 34.3 grams, of sodium in 4.00 hours.

The consequences of this calculation are interesting. We would have to
run this electrolysis for more than two days to prepare a pound of
sodium.

Exercise:
1. In the electrolysis of a gold sample to obtain gold, the half reaction at
the cathode is
Au
3+
+ 3e Au(s)
What mass of gold can be deposited at the cathode in 1.00 hour by a
current of 1.50A?
2. How many grams of silver are deposited at a platinum cathode in the
electrolysis of AgNO
3
(aq) by 1.73A of electric current in 2.05 hr?
3. How many coulomb of electric charge are required to deposit 25.0 g
Cu(s) at the cathode in the electrolysis of CuSO
4
(aq)
4. For how many minutes must the electrolysis of a solution of
CuSO
4
(aq) be carried out, at a current of 2.25A, to deposit 1.00g of
Cu(s) at the cathode?