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CHAPTER 6: ELECTROCHEMISTRY

6.1 ELECTROLYTES AND NONELECTROLYTES


Electrolytes

Non-electrolytes

Substances that
can conduct
electricity when they
are in molten state
or aqueous solution
and undergo
chemical changes.

Substances that
cannot conduct
electricity either in
molten state or
aqueous solution.

6.1 ELECTROLYTES AND NONELECTROLYTES


Electrolytes

Non-electrolytes

Example:
Sodium chloride,
NaCl solution
Molten Lead (II)
bromide, PbBr2

Example:
Naphthalene
Glucose solution
All covalent
compounds

All ionic compounds

6.1 ELECTROLYTES AND NONELECTROLYTES


Electrolytes

Non-electrolytes

Contain freely
moving ions.

Contain neutral
molecules
Do not contain freely
moving ions.

6.2 ELECTROLYSIS OF
MOLTEN COMPOUND
What is electrolysis?

process whereby the ionic


compounds in molten or
aqueous state are broken
down into constituent
elements by passing
electricity through them.

BATTERY
Electrodes
CATHODE

Electrode which
is connected
to the negative
terminal

ANODE

ELECTROLYTE

Electrode which
is connected to
the positive
terminal

Molten PbBr2
Pb2+ ions, Br- ions

Passing
electric

BrIon move to..

ANODE
Release electrons
2Br- Br2 + 2e-

Brown gas produced

Pb2+
Ion move to..

CATHODE
Accept electrons
Pb2+ + 2e- Pb

Grey globules produced

PbBr2

Pb 2+

Br-

ANODE
Release electron
2Br- Br2 + 2eHalf equation
Overall ionic equation

CATHODE
Accept electron
Pb2+ + 2e- Pb
Pb2+ + 2e-

Pb

2Br- Br2 + 2e-

Pb2+ + 2Br- Pb + Br2

Factors affecting the


products of electrolysis
for aqueous solution
A.Position of ions in the
Electrochemical Series
B.The Concentration of the
solution
C.The type of Electrodes

A. Position in the Electrochemical Series

The lower position


of the ion in the
Electrochemical
Series, the easier
the ion to be
discharged during
electrolysis

A. Position in the Electrochemical Series


CuSO4 solution
Cu2+, H+,SO42- OH-.

Anode

Cathode

The anions, OH
and SO42- move
to the anode.
OH- ions are
selectively
discharged.
Bubbles of
colourless gas is
released.

4OH- (aq) 2H2O(l) + O2 (g) + 4e-

Copper(II)
sulphate The cations,
solution
Cu2+.and H+
move to the
cathode.
Cu2+ ions accept
two electrons.
Brown solid is
formed at the
cathode.
Cu2+ (aq) + 2e- Cu (s)

The overall ionic equation :


2Cu2+ (aq) + 4OH-(aq) 2Cu (s) + 2H2O(l) + O2 (g)

B. The Concentration of the solution

Example : Concentrated hydrochloric acid consists of


H+, Cl-,OH-.

Anode
The anions,OHand Cl- move to
the anode.
Cl- ions are
selectively
discharged
because
concentration of
Cl- is higher than
OH Bubbles of
yellowish gas is
produced.
2Cl- Cl2+ 2e

Cathode
The cations,
H+ ions move
to the
cathode.
H+ ions
accept
electron.
Bubbles of
Colourless
gas is
produced.
2H+ + 2e H2
The overall ionic equation :
2H+ (aq) + 2Cl-(aq) Cl2 (g) + H2 (g)

C. The Type of Electrodes (Carbon electrodes)

Anode
OH- and SO42move to the
anode.
OH- ions are
selectively
discharged due
to the lower
position in ECS.
Bubbles of
colourless gas is
released at the
anode.
4OH- 2H2O + O2 + 4e-

Using Carbon Electrode

Carbon

Carbon

Observation :
The blue copper(II)
sulphate solution becomes
faded/paler because the
concentration of
copper(II)ions decreases.

Cathode
Cu2+.and H+
move to the
cathode.
Cu2+ ions
selectively
discharged
because Cu2+is
lower than H+
in ECS
Brown
deposit/solid is
produced
Cu2+ + 2e Cu

The overall ionic equation :


2Cu2+ (aq) + 4OH-(aq) 2Cu (s) + 2H2O(l) + O2 (g)

C. The Type of Electrodes (Copper electrodes)

Anode

Cathode

Copper : active
electrode.
Copper
electrode
dissolved and
release
electrons to
form copper(II)
ion.
Copper
electrode
becomes
thinner// Size
of anode
decreaces

Cu Cu

2+

+ 2e

Using Copper Electrode Cu2+.and H+


Copper

Observation :

Copper

The blue colour


copper(II) sulphate
solution remains
unchanged because the
rate of discharge of
Cu2+ ions at cathode is
equal with the rate of
formation of Cu2+ at
anode.

move to the
cathode.
Cu2+ ions
selectively
discharged
because Cu2+ is
lower than H+
in ECS
Copper electrode
become
thicker//Size of
cathode
increases
Cu2+ + 2e- Cu

INDUSTRIAL APPLICATIONS OF ELECTROLYSIS

A. Extraction of Aluminium

The main source of aluminium is bauxite ore (Aluminium Oxide),


the melting point of aluminium oxide is very high (over 2 000C),
Cryolite (Na3AIF6) is added to lower the melting point to 980oC.
Anode : 2O2- O2 + 4e

Cathode : Al3+ + 3e Al

B. Purification of Copper
The impure copper plate is connected to the +ve terminal anode.
The pure copper plate is connected to the ve terminal cathode.
The electrolyte : copper(II) sulphate solution.

Anode : Cu Cu2+ + 2e

Deposit at
the bottom
of the
beaker

Cathode : Cu2+ + 2e Cu

Pure
cooper

C. Electroplating
Coating with a Thin Protective Layer of Metal.

Anode : Cu Cu2+ + 2e

Cathode : Cu2+ + 2e Cu
Blue
solution
remains
unchanged

Copper
Dissolves/
becomes
thinner

Coated/
deposit layer of
brown solid

VOLTAIC CELLS
[GALVANIC CELL]
A simple voltaic cell is a cell with two different
metals being immersed into an electrolyte and
connected by wire
It converts chemical energy to electrical energy.

MECHANISM OF SIMPLE VOLTAIC CELL


Anode (-ve)

Cathode(+ve)

More electropositive metal in Less electropositive metal in


Electrochemical Series
Electrochemical Series
Release electrons

Accept electrons

Electrons are flow through the external circuit towards the


copper plate.

Daniell cell using a


porous pot

Daniell cell using a


salt bridge

- Daniell cell is a voltaic cell.


- Electrodes - Zinc (anode) and copper (cathode)
- The two solutions are separated by the porous pot/salt bridge
-A salt bridge is made from a filter paper soaked in a saturated solution
that will not react with the two electrolytes.
-The common electrolyte used are or a solution of sodium or potassium
salts.

FUNCTIONS OF
SALT BRIDGE OR POROUS
POT :
(a)

To prevents the two


electrolytes from mixing.

(b)

To allow the flow of ions so


that the electric circuit is
completed.

MECHANISM OF DANIELL
Cathode
CELL Anode
Electrode becomes thinner

Electrode becomes thicker

Metal releases electrons


Zn Zn2+ + 2e-

Metals ion accepts electrons


Cu2+ + 2e- Cu

The concentration of copper(II) sulphate solution


decreases. The blue colour of the solution becomes paler.
The overall ionic equation in Daniell cell is:
Zn + Cu2+ Zn2+ + Cu

Various types
of
voltaic cell

Lead acid
Accumulator

Dry cell

Mercury cell

Alkaline cell

Nickel-cadmium
cell

Advantages
Rechargeable
Can be made
to have
higher voltage

Portable
Cheap
Stable voltage
of 1.5 v

Portable

Portable
Voltage of
1.5 V
More long
lasting

Disadvantages
Heavy
Expensive
Spilled easily

Not
rechargeable

Not rechargeable
Produces voltage
of 1.3 V only
Poisonous

Not
rechargeable
May leak

Portable
Rechargeable
up to hundreds
of times

Produce low
voltage of 1.25 V
Expensive
Heavy

SIMILARITIES BETWEEN AN
ELECTROLYTIC CELL AND A VOLTAIC
CELL

Consists of an electrolyte, an anode and a cathode


Electrons flow from the anode to the cathode in the
external circuit

DIFFERENCES
AN ELECTROLYTIC
CELL AND A VOLTAIC
Electrolytic
cell BETWEEN
Type
of cell
Voltaic
cell
CELL:

Electrical energy
Chemical energy
From positive terminal
to negative terminal
Cathode:
Accepts electrons

Anode :
Releases electrons
Two similar
(usually carbon) or
different metals

Conversion of
energy
Flow of

Chemical energy
electrical energy

electrons

From negative terminal


to positive terminal

Negative
terminal

Anode:
Release of electrons

Positive

Cathode:

terminal
Types of
electrodes

Accepts electrons

Two different metals

THE ELECTROCHEMICAL SERIES ~


An arrangement of metals based on the ability
of each metal atom to release electrons.

The higher the position of a metal in the


electrochemical series, the greater the ability of the
metal atoms to release electrons, and the more
electropositive is the metal.

Metals

Cations

K K e

Na Na e

Ca Ca2 2e
Mg Mg2 2e
Al Al 3 3e
Zn Zn2 2e
Fe Fe 2 2e
Sn Sn2 2e
Pb Pb2 2e
H H e
Cu Cu2 2e
Ag Ag e

Ability of
metal
atoms to
release
electrons
to form
ions
decreases

Ability of
cations to
accept
electrons to
form
metals
increases

THE CONSTRUCTION OF THE


ELECTROCHEMICAL SERIES IS BASED ON :

1) The potential difference between


two metals in a voltaic cell.
2) The ability of a metal to displace
another metal from its salt
solution.

1) THE POTENTIAL DIFFERENCE BETWEEN TWO


METALS

In a voltaic cell, two different metals are used


to create a potential difference, shown by the
reading of the voltmeter.
The further apart the two metals are in the
electrochemical series, the greater the voltage
produced by the cell.

The metal which is higher in the electrochemical


series will be the negative terminal.
The metal which is lower in the electrochemical
series will be the positive terminal

Electrons flow from negative to positive metal through


the external circuit.

Voltmeter
Electron flow

Showing the flow of


electrons

Copper strip

Magnesium strip
Mg Mg

2+

Cu2+ + 2e Cu

+ 2e
Copper(II) sulphate,
CuSO4 solution

Overall ionic equation : Mg + Cu2+ Cu + Mg2+

2) THE ABILITY OF A METAL TO DISPLACE


ANOTHER
METAL FROM ITS SALT SOLUTION

A metal which is higher in the electrochemical series is


able to displace a metal below it in the
electrochemical series from its salt solution.
Example :
Zinc can displace copper from copper(II) sulphate
solution.
Zn + CuSO4 Cu + ZnSO4

THE IMPORTANCE OF THE


ELECTROCHEMICAL SERIES
1.
2.
3.

To determine the terminals of voltaic


cells
To compare the standard voltage of the
voltage cell
To predict the ability of metal to
displace another metal from its salt
solution

EXAMPLE :
Figure below shows the cell voltages of a few voltaic cells using
different metals as electrodes.

Predict the negative terminal, positive terminal and cell voltage of the
following voltaic cells.
Voltaic cells

Negative terminal Positive terminal

Cell voltage/V

Mg/Ag
Mg/Zn
Zn/Pb

Magnesium
Magnesium

Silver
Zinc

Zinc

Lead

3.0 + 0.5 = 3.5


3.0 1.1 = 1.9
1.1 0.4 = 0.7

THE IMPORTANCE AND EFFECTS


OF ELECTROCHEMICAL
The importance of electrochemical industries in our
INDUSTRIES
daily life is as follows:
Oxygen gas, chlorine gas can be produced by
electrolysis.
Electroplating are widely used to prevent corrosion
and enhance the appearance of the materials.
The industrial manufacture of batteries produces
various types of cells and batteries in different shapes
and sizes.

The pollution caused by the electrochemical


industries are as follows:
The electroplating industries produce pollutants such
as poisonous heavy metal ions and poisonous cyanide
ions.
The use of mercury electrodes in electrolysis can
cause air and water pollution.

Thus, the waste should be treated and


disposed of in a safe and orderly manner.