INTRODUCTION TO ELECTROLYSIS

TERMS
Electrolysis is the process of electrically inducing chemical changes in a conducting melt or
solution eg splitting an ionic compound into the metal and non-metal.

Conductors are materials carry an electric current via freely moving electrically charged
particles, when a potential difference (voltage!) is applied across them.

Any molten or dissolved material in which the liquid contains free moving ions is called the
Electrolyte.

Compounds that dissociate to a large extent (70 to 99%) into ions when dissolved in water
are classified as Strong Electrolytes.

Compounds that dissociate to a small extent are termed Weak Electrolytes.

Ions are charged particles eg Na+ or Cl- and their movement or flow constitutes an electric
current.
INTRODUCTION TO ELECTROLYSIS
Ionic Solutions conduct a Current
INTRODUCTION TO ELECTROLYSIS
Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 215
Source of
electric power
Free ions
present
in water
Pure water does not conduct an
electric current
INTRODUCTION TO ELECTROLYSIS
Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 215
Source of
electric power
Pure
water
Electrolytes
INTRODUCTION TO ELECTROLYSIS
Copyright 2007 Pearson Benjamin Cummings. All rights reserved.
(a) Nonelectrolyte (b) Weak electrolyte (c) Strong electrolyte
Electrolytes
INTRODUCTION TO ELECTROLYSIS
Timberlake, Chemistry 7
th
Edition, page 290
Electrolytes - solutions that carry an electric current
NaCl(aq) Na
+
+ Cl
-
HF(aq) H
+
+ F
-
strong electrolyte weak electrolyte nonelectrolyte
What does the Complete Electrical Circuit
consist of?
-Positive cations eg Na+ attracted to the negative cathode
electrode.
-Negative anions eg Cl- attracted to the positive anode
electrode,
- No electrons flow in electrolyte they flow in metal wires
or graphite.
The circuit of 'charge flow' is completed by the electrons
moving around the external circuit eg copper wire, metal or
graphite electrode, from the positive to the negative
electrode
The molten or dissolved materials are usually acids,
alkalis or salts and their electrical conduction is usually
accompanied by chemical changes eg decomposition.
INTRODUCTION TO ELECTROLYSIS
INTRODUCTION TO ELECTROLYSIS
Ionic solid do not allow electric current to pass
through, the ions are too tightly held by chemical
bonds and can't flow from their ordered situation!
When an ionically bonded substances are melted
or dissolved in water the ions are free to move
about.
Some covalent substances dissolve in water and
form ions.
eg hydrogen chloride HCl, dissolves in water to form 'ionic'
hydrochloric acid H
+
Cl
-
(aq)

INTRODUCTION TO ELECTROLYSIS
ELECTROLYSIS SPLITS A COMPOUND:

Electrolyte can be broken down (decomposed)
into simpler substances by passing an electric
current through them.
Since it requires an 'input' of energy, it is an
endothermic process.
During electrolysis in the electrolyte ...
positive metal or hydrogen ions move to the
negative electrode (cations attracted to cathode).
negatively charged ions move to the positive
electrode (anions attracted to anode)

INTRODUCTION TO ELECTROLYSIS
During electrolysis,. metals and hydrogen are formed at the negative
electrode from positive ions by electron gain (reduction),
Cu
2+
+ 2e- ==> Cu
Non-metals eg oxygen, chlorine, bromine etc. are formed from
negative ions changing on the positive electrode by electron loss
(oxidation),
2Cl
-
==> Cl
2
.
+
-2e-
In a chemical reaction, if an oxidation occurs, a reduction
must also occur too (and vice versa) so these reactions
'overall' are called redox changes.
INTRODUCTION TO ELECTROLYSIS
MECHANISM OF ELECTROLYSIS
Electrolysis is a redox reaction as it involves
transfer of electrons.
Oxidation occurs at anode where anion lose
electrons
Reduction occurs at cathode where cations
accepts electrons
Metal or hydrogen gas are discharged at
cathode
Non- metals are discharged at anode.
INTRODUCTION TO ELECTROLYSIS
Before the passage of current the ions are
wondering randomly in electrolyte. As the
direct current passes through the anions in
the electrolyte move towards the anode
where they give up their electron to become
neutral, The electron then move from the
anode through the battery and external circuit
to the cathode. At the same time the cation in
the electrolyte migrate to the cathode where
they take up the excess electrons to become
electrically neutral.

INTRODUCTION TO ELECTROLYSIS
ELECTROLYSIS OF MOLTEN LEAD II BROMIDE
INTRODUCTION TO ELECTROLYSIS
Electrolyte: Molten lead (II) bromide.
Electrode: carbon ( inert )
Ions present: Pb
2+
+ 2Br
1-
Reaction at cathode ( negative electrode)

Pb
2+
+ 2 e ----------------- Pb

Reaction at anode (positive electrode)

2Br
1-
----------------- Br
2
+ 2e
.
The over all reaction:

PbBr
2

(l)
----------------- Pb
(l)
+ Br
2

(g)

INTRODUCTION TO ELECTROLYSIS
FACTORS EFFECTING SELECTIVE/
PREFERENTIAL DISCHARGE OF IONS
During electrolysis the product formed depends on the nature of
electrolyte.
If electrolyte is a solution, the product formed at the electrodes may vary
because the solvent which is water will also ionize.
The product which is formed at the electrode will depend on wheather it
is the ion from the electrolyte or solvent which is being discharged at the
electrode.
This depends on the
Position of the ion in the electrochemical
series
Concentration of the ion in the electrolyte
Nature of the electrode.

INTRODUCTION TO ELECTROLYSIS
POSITION OF IONS IN THE ELECTROCHEMICAL SERIES

INTRODUCTION TO ELECTROLYSIS
If all the other factors are constant, a cation which is lower in
the series( less electropositive) will show a greater tendency to
discharge then the ion which is higher up in the series because
less electropositive can gain electrons more readily from the
cathode to become neutral while more electropositive tend to
persist in solution as a positive ion.
Thus K
+
, Na
+
, Ca
2+
, Mg
2+,
Al
3+
may never be discharged at all
from aqueous solution since H+ will discharge first.
An anion which is higher in the series (less electronegative) is
discharged in preference to anion which is lower down in
series ( more electronegative). Less electronegative loses
electrons more readily
Thus SO
4
2-
, NO
3
-
are never discharged from the aqueous
solution due to preferential discharge of OH-
RELATIVE CONCENTRATION OF THE IONS IN THE SERIES
INTRODUCTION TO ELECTROLYSIS
Some times the order of discharge as indicated by
electrochemical series may be reversed by the
concentration effect because increasing the
concentration of a given ion tends to promote its
discharge from the solution where other conditions
are kept constant.
It is effective only if the two rival ions are closely
positioned in the series. The further apart they are
the less important is the effect of concentration.
Example: In electrolysis of NaCl solution, at
cathode Cl
-
ions is preferentially discharged
although OH
-
ions are high up the series. The
effect of concentration is predominant due to
closeness of the position of Cl
-
& OH
-
in series
NATURE OF ELECTRODES
INTRODUCTION TO ELECTROLYSIS
In electroysis of brine if platinum or graphite cathode is used the H
2

gas is displaced but if mercury cathode is used then sodium will
associate with mercury cathode to form sodium amalgum and
discharged. This method is used in industrial manufacturing of
NaOH.

Na
+
(aq)
+ Hg
(l)
+ e -------- Na/Hg
(l)

If Cu anode is used in solution of CuSO
4
then neither SO
4
2-
nor
OH
-
will be discharged instead the atoms from the anode will go into
solution as Cu
2+
because these atoms will give up their electrons
more readily then SO
4
2-
or OH
-
. This principal is made use in the
extraction and purification of some metals.
Electrolysis of Brine
INTRODUCTION TO ELECTROLYSIS
Sodium chloride solution
gives equal volumes of
hydrogen gas at cathode and
green chlorine gas at anode
with sodium hydroxide left in
solution. However in dilute
solution, oxygen gas as well as
chlorine gas is produced
INTRODUCTION TO ELECTROLYSIS
Electrolyte: Aqueous Sodium chloride
Electrodes: Carbon / Copper
Ions present: H
+
, OH
-
, Na
+
, Cl
-
.

Reaction at cathode ( negative electrode)
2H
+
+ 2e --------------------- H
2

(g)


Reaction at anode ( positive electrode)

2Cl
-

(aq)
-------------------- Cl
2
+ 2e
.
Over all reaction

2NaCl
(aq)
+ H
2
O
(l)
------- H
2(g)
+ Cl
2(g)
+ NaOH
(aq).

Electrolysis of Concentrated HCl
INTRODUCTION TO ELECTROLYSIS
Electrolyte: Aqueous Hydrochloric acid
Electrodes: Carbon / Copper
Ions present: H
+
, OH
-
, Cl
-
.
Reaction at cathode ( negative electrode)

2H
+
+ 2e --------------------- H
2

(g)


Reaction at anode ( positive electrode)

2Cl
-

(aq)
-------------------- Cl
2
+ 2e
.
Over all reaction

2HCl
(aq)
---------------------- H
2(g)
+ Cl
2(g)
Electrolysis of Dilute Sulphuric Acid
INTRODUCTION TO ELECTROLYSIS
INTRODUCTION TO ELECTROLYSIS
Electrolyte: Aqueous Sulphuric acid
Electrodes: Carbon / Copper
Ions present: H
+
, OH
-
, SO
4
2-
.
Reaction at cathode ( negative electrode)
2H
+
+ 2e --------------------- H
2

(g)
Reaction at anode ( positive electrode)
4OH
-
(aq)
-------------------- O
2

(g)
+ 2H
2
O
(l)
+ 4e-
Over all reaction
2H
2
O
(l)
---------------------- 2H
2(g)
+ O
2(g)
ELECTROLYSIS OF WATER
INTRODUCTION TO ELECTROLYSIS
Electrolysis of Copper (II) Sulphate Solution
using Copper Electrodes
INTRODUCTION TO ELECTROLYSIS
INTRODUCTION TO ELECTROLYSIS
Copper(II) sulphate with copper
electrodes, the copper deposits at
cathode and the copper dissolves from
anode. The blue colour of the Cu
2+

ions stays constant because Cu
deposited = Cu dissolved.
INTRODUCTION TO ELECTROLYSIS
Electrolyte: Aqueous Copper sulphate solution
Electrodes: Copper metal
Ions present: H
+
, OH
-
, Cu
2+
, SO
4
2-

.
Reaction at cathode ( negative electrode)

Cu
2+
+ 2e --------------------- Cu (s)

Reaction at anode ( positive electrode)

Cu
(s)
-------------------- Cu
2+
(aq)
+ 2e
Copper metal of anode will dissolve and added in electrolyte.

This method is used to refine copper.
Electrolysis of Copper (II) Sulphate Solution
using Graphite Electrodes
INTRODUCTION TO ELECTROLYSIS
Electrolyte: Aqueous Copper sulphate solution
Electrodes: Graphite
Ions present: H
+
, OH
-
, Cu
2+
, SO
4
2-
.

Reaction at cathode ( negative electrode)

Cu
2+
+ 2e --------------------- Cu
(s)

.
Reaction at anode ( positive electrode)

4OH
-
(aq)
----------------------- O
2(g)
+ 2H
2
O
(l)
+ 4e
.
ELECTROLYSIS PRODUCT USING INERT
ELECTRODES
INTRODUCTION TO ELECTROLYSIS
ELECTROLYTE IONS IN
SOLUTION
PRODUCT AT
CATHODE
PRODUCT AT
ANODE
Conc. HCl H
+
(aq)
Cl
-
(aq)

Hydrogen gas
Chlorine gas
Conc. NaCl sol. Na
+
(aq)
Cl
-
(aq)

Hydrogen gas from
water
Chlorine gas
Dilute H
2
SO
4
H
+
(aq)
SO
4
2-
(aq)


Hydrogen gas
Oxygen from
water
CuSO
4
sol. Cu
2+

(aq)
SO
4
2-
(aq)

Copper metal
Oxygen from
water
INTRODUCTION TO ELECTROLYSIS
CATIONS PRODUCT AT CATHODE ANIONS `PRODUCT AT ANODE
K
+
Na
+
Ca
2+
Mg
2+
Al
3+


Ni
2+
Pb
2+
H
+
Cu
2+
Ag
+

Hydrogen gas from
water




Nickle
Lead
Hydrogen
Copper
Silver

Cl
-
Br
-
I
-



SO
4
2-
NO
3
-
Chlorine
Bromine
Iodine



Oxygen from water

Oxygen from water
ELECTROPLATING
INTRODUCTION TO ELECTROLYSIS
The coating of a metal object with
another metal object is called
Electroplating. It is carried out in a cell
called plating bath. It contains an
electrolyte. For silver plating electrolyte
is a solution of silver salt. The article to
be plated is made the cathode in the cell
so that metal ions move to it when
current is switched on
INTRODUCTION TO ELECTROLYSIS
EXTRACTION OF METALS BY
ELECTROLYSIS
INTRODUCTION TO ELECTROLYSIS
The steps involved in extracting a metal include the
following:

concentrating the ore, and chemically treating it if
necessary
reducing the mineral to free metal
refining and purifying the metal.
CONCENTRATION & CHEMICAL
TREATMENT OF ORE
INTRODUCTION TO ELECTROLYSIS
Floatation Method

Metal sulfide ores are concentrated by flotation,
a process that exploits differences in the ability
of water and oil to wet the surfaces of the
mineral . Mineral particles float to the top of
the tank along with soapy air bubbles, while the
gangue sinks to the bottom
. Ores are complex mixtures of metal-containing
material and useless impurities called gangue.
INTRODUCTION TO ELECTROLYSIS
Chemical Method
INTRODUCTION TO ELECTROLYSIS
.Ores can also be concentrated by chemical means. In the
Bayer process, the Al
2
O
3
in bauxite is separated from
Fe
2
O
3
impurities by treating the ore with NaOH.

Roasting, or heating in air, is another chemical
treatment used to convert minerals to
compounds that are more easily reduced to the
metal.
ELECTROLYSIS OF MOLTEN BAUXITE
INTRODUCTION TO ELECTROLYSIS
The purified bauxite ore of aluminium oxide is continuously
fed in. Cryolite is added to lower the melting point and
dissolve the ore.
When the d.c. current is passed through aluminium forms at
the positive cathode and sinks to the bottom of the tank.
At the negative anode, oxygen gas is formed.
This is quite a problem. At the high temperature of the
electrolysis cell it burns and oxidises away the carbon
electrodes to form toxic carbon monoxide or carbon dioxide.
So the electrode is regularly replaced and the waste gases
dealt with!
It is a costly process (6x more than Fe!) due to the large
quantities of expensive electrical energy needed for the
process.
INTRODUCTION TO ELECTROLYSIS
INTRODUCTION TO ELECTROLYSIS

Electrolyte: Molten Aluminum oxide
Electrodes: Carbon
Ions present: Al
3+
& O
2-

Reaction at cathode (positive electrode)

4Al
3+
+ 12 e ----------------- 4Al
(l)
.Reaction at anode (negative electrode)

6O
2-
----------------- 3O
2
+ 12e.
The over all reaction:
Aluminum oxide ------------- Molten Aluminum + oxygen gas
4Al
2
O
3

(l)
----------------- 4Al
(l)
+ 6O
2

(g)
It is a very endothermic process.

INTRODUCTION TO ELECTROLYSIS
INTRODUCTION TO ELECTROLYSIS

Anodizing of Aluminium

Aluminium can be made more resistant to
corrosion by a process called anodizing.
Aluminium is a reactive metal but it is resistant
to corrosion. This is because aluminium reacts in
air to form a layer of aluminium oxide which
then protects the aluminium from further attack.

This is why it appears to be less reactive than its position in the reactivity
series of metals would predict.
INTRODUCTION TO ELECTROLYSIS




For some uses of aluminium it is desirable to increase
artificially the thickness of the protective oxide layer in a
process is called anodizing.
This involves removing the oxide layer by treating the
aluminium sheet with sodium hydroxide solution.
The aluminium is then placed in dilute sulphuric acid and
is made the positive electrode (anode) used in the
electrolysis of the acid.
Oxygen forms on the surface of the aluminium and
reacts with the aluminium metal to form a thicker
protective oxide layer.


SIMPLE CELL & BATTERY
INTRODUCTION TO ELECTROLYSIS
The chemistry of simple cells or batteries is in
principle the opposite of electrolysis.
A redox reaction occurs to produce products
and energy is given out. It is exothermic, BUT
the energy is released as electrical energy and the
system shouldn't heat up.
A simple cell can be made by dipping two
different pieces of metal (of different reactivity)
into a solution of ions e.g. a salt or dilute acid.
The greater the difference in reactivity, the
bigger the voltage produced
DANIEL CELL
It uses a half-cell of copper dipped in copper(II)
sulphate, in electrical contact with a 2nd half-cell of
zinc dipped in zinc sulphate solution.
The zinc is the more reactive, and is the negative
electrode, releasing electrons because on it zinc
atoms lose electrons to form zinc ions,
Zn
(s)
==> Zn
2+
(aq)
+ 2e-
The less reactive metal copper, is the positive
electrode, and gains electrons from the negative
electrode through the external wire connection and
here the copper(II) ions are reduced to copper atoms.
INTRODUCTION TO ELECTROLYSIS
DANIEL CELL
Cu
2+
(aq)
+ 2e- ==> Cu
(s)

Overall the reactions is:
Zn
(s)
+ CuSO
4(aq)
+ ZnSO
4(aq)
+ Cu
(s)
ionically: Zn
(s)
+ Cu
2+
(aq)
+ Zn
2+
(aq)
+ Cu
(s)

The bigger the difference in reactivity, the bigger
the cell voltage produced
Cells or batteries are useful and convenient
portable sources of energy.

INTRODUCTION TO ELECTROLYSIS
DANIEL CELL
INTRODUCTION TO ELECTROLYSIS
LEAD ACCUMULATOR
INTRODUCTION TO ELECTROLYSIS
INTRODUCTION TO ELECTROLYSIS
DRY CELL
INTRODUCTION TO ELECTROLYSIS
. Fuel Cells

Hydrogen gas can be used as fuel.
It burns with a pale blue flame in air reacting with
oxygen to be oxidised to form water.
hydrogen + oxygen ==> water
It is a non-polluting clean fuel since the only
combustion product is water.
It would be ideal if it could be manufactured by
electrolysis of water eg using solar cells.
Hydrogen can be used to power fuel cells.
It all sounds wonderful BUT, still technological
problems to solve for large scale manufacture and
distribution of 'clean' hydrogen gas or use in
generating electricity AND its rather an
inflammable explosive gas!
INTRODUCTION TO ELECTROLYSIS
Fuel cells are 'battery systems' in which two
reactants can be continuously fed in. The
consequent redox chemistry produces a working
current.
Most fuel cells use hydrogen, but alcohols and
hydrocarbons can be used.
A fuel cell works like a battery but does not run down
or need recharging as long as the 'fuel' supply is
there.
It will produce electricity and heat as long as fuel
(hydrogen) is supplied.

INTRODUCTION TO ELECTROLYSIS
Fuel Cell
INTRODUCTION TO ELECTROLYSIS
Potassium
Hydroxide
Solution
H
2
O
2
anode cathode
OVERALL EQUATION
?
Click on labels and ?s for further information
? ?
ANODE
POROUS CARBON
WITH NICKEL (CATALYST)


2H
2
(g) +4OH
-
(aq) 4H
2
O (l) + 4e
-

INTRODUCTION TO ELECTROLYSIS
Half Equation
CATHODE
POROUS CARBON
WITH NICKEL & NICKEL OXIDE (CATALYST)


O
2
(g) + 2H
2
O (l) + 4e
-
4OH- (aq)
INTRODUCTION TO ELECTROLYSIS
Half Equation
OVERALL EQUATION
2H
2
(g) + O
2
(g) 2H
2
O (aq)

about 70% efficiency
INTRODUCTION TO ELECTROLYSIS
INTRODUCTION TO ELECTROLYSIS
A fuel cell consists of two electrodes consisting of an
anode and a cathode) which are sandwiched around
an electrolyte (conducting salt/acid/alkali solution of
free ions).
Hydrogen is fed to the anode, and oxygen is fed to
the cathode.
The platinum catalyst activates the hydrogen
atoms/molecules to separate into protons (H+) and
electrons (e-), which take different paths to the (+)
cathode.
INTRODUCTION TO ELECTROLYSIS
The electrons go through an external circuit,
creating a flow of electricity eg to light a bulb.
The protons migrate through the electrolyte and
pass through the semi-permeable membrane to
the cathode, where they reunite with oxygen and
the electrons to produce water.
Each cell only produces a small voltage
(0.4V?) so many cells can be put together in
series to give a bigger working voltage.

INTRODUCTION TO ELECTROLYSIS
Reverse Action
If there is spare electricity from another source
available, you can run the fuel cell in reverse and
electrolyze the water to make hydrogen and
oxygen (acting as an electrolyser).
The two gases are stored, and when electricity or
heat needed, the fuel cell can then be re-run using
the stored gaseous fuel.
this is called a regenerative fuel cell system.
You can use solar energy from external panels on
the space shuttle to do this, and use the fuel when
in the 'darkness of night'.
INTRODUCTION TO ELECTROLYSIS
Equation Summary of HYDROGEN OXYGEN Fuel
Cell
Oxidation (at anode)
2H
2(g)
==> 4H
+
(aq)
+ 4e-
Reduction (at cathode)
O
2(g)
+ 4H
+
(aq)
+ 4e
-
==> 2H
2
O
(l)
Overall Equation
2H
2(g)
+ O
2(g)
==> 2H
2
O
(l)
INTRODUCTION TO ELECTROLYSIS


THE END
INTRODUCTION TO ELECTROLYSIS