ELECTROLYSIS

Mohamad nasir bin othman

INTRODUCTION
In contrast to spontaneous
redox reaction, which result in
the conversion of chemical
energy into electrical energy,
electrolysis is the process in
which electrical energy is used
to cause a non-spontaneous
chemical reaction to occur.
An electrolytic cell is an
apparatus for carrying out
electrolysis. The same
principle underlie electrolysis
and the processes that take
place in galvanic cells.

Electrolyte cell
The electrolyte cell contains a pair of
electrode connected to the battery.
The battery serves as an electron pump,
driving electrons to the cathode, where
reduction occurs, and withdrawing electrons
from the anode, where oxidation occurs.

The reactions at the electrodes are,

Anode (oxidation): 2Cl
-
(l) Cl
2
(g) + 2e
Cathode (reduction) 2Na
+
(l) + 2e 2Na(l)
Overall: 2Na
+
(l) + 2Cl
_
(l) 2Na(l) + Cl
2
(g)
Electrolysis of Water
19.8
Anode: 2H
2
O (l) O
2
(g) + 4H
+
(aq) + 4e
-

Cathode: 4H
+
(aq) + 4e 2H
2
(g)
2H
2
O (l) 2H
2
(g) + O
2
(g)
Electrolysis
Electrolysis of molten
compounds
Metals are formed at the cathode
Non-metals are formed at the
anode
Electrolysis of aqueous
solution
Selective discharge of ions determined by:
Position of ions in the electrochemical series
Concentration of ions
Types of electrodes

Electrolysis of molten compounds

Example 1 : PbBr
2

Anode:

?

Katode: ?






a. Position of ions in the electrochemical
series

The lower the position
of the ion in the
electrochemical series,
the easier the ion will
be discharged.
Example: Electrolysis of
aqueous sodium sulphate
(Na
2
SO
4
).


Na
2
SO
4
2Na
+
+ SO
4
2-

H
2
O = H
+
+ OH
-

Anode : ?
Cathode: ?
Cation Anion
K
+

Na
+

Mg
2+

Al
3+

Zn
2+

Fe
3+

Sn
2+

Pb
2+

H
+

Cu
2+

Hg
+

Ag
+

F
-

SO
4
2-

NO
3
-

Cl
-

Br
-

I
-

OH
-


Tendency
to
discharge
increases
b. Effect of concentration of ions in the
solution, CuCl
2
(aq)
CuCl
2
Cu
2+

+ 2Cl
-


H
2
O H
+

+ OH
-

Anode: ?
Cathode: ?
c. Effect of types of electrode used
Electrolysis of CuSO
4
solution
CuSO
4
Cu
2+

+ SO
4
2-


H
2
O H
+

+ OH
-

(a) If carbon is used as the electrodes, OH
-

ions are
discharged at the anode because of the position of OH
-


ion in the electrochemical series.
(b) if Cu is used as the anode,both SO
4
2-

and OH
-

ions
are not discharged. Cu acts as an active electrode here
because it takes part in the chemical reaction during
electrolysis.

Quantitative aspects of electrolysis
The quatitative treatment
of electrolysis was
developed primarily by
Faraday.
He observed that the mass
of product formed (or
reactant consumed) at an
electrode is proportional to
both the amount of
electricity transferred at the
electrode and the molar
mass of the substance in
question.
The amount of electricity transferred is measured
in the unit of coulomb (C).
One coulomb is the quantity of electric charge
transferred by a current of one ampere (A) in one
second (c). Thus,
Q = It
Q : quantity of electric charge (C)
I :current (A)
t : time (s)
Faraday constant (F)
Faraday constant (F) is the charge on one mole
of electrons, that is
1 F = 96500 C
Faradays First Law
Faradays First Law states that the mass of a
substance produced at an electrode during
electrolysis is proportional to the quantity of
electricity (in coulomb) passed.
Example 1
An aqueous solution of copper(II)sulphate is
electrolysed using a current of 0.150A for 5
hours. Calculate the mass of copper deposited
at an electrode at the cathode.

Q = it = 0.150 x 5 x 3600 = 2700 C
Number of moles of electrons = 2700/96500 = 0.028 mol
Number of moles of copper deposited= x 0.028 = 0.014 mol
Mass of copper deposited = 0.014 x 63.5 g = 0.889 g
Faradays Second Law
If the same quantity of
electricity is passed
through different
electrolytes, the mass of
the substance liberated at
the electrode is inversely
proportional to the
charges on the ions.
Thus, 1F of electricity will
discharge 1 mole of Ag
+


ions, but mole of Cu
2+


ions, 1/3 mole of Al
3+

ions
and mole of oxygen gas.
We can determine the mass of a substance
deposited at an electrode by weighing the
electrode before and after the electric current
Is supplied. The apparatus used for this type of
experiment is called coulometer.
The apparatus on the right is called a voltameter. A voltameter is
an electrolyte cell which is set up for collecting and measuring
the volume of any gas liberated during the electrolysis.
Figure 1
Example 2
With reference to Figure 1,
calculate
(a) the mass of copper
deposited
(b) the volume (in dm
3
)of
hydrogen liberated
(c) the volume (in cm
3

)of oxygen
collected at room temperature
and pressure, if 0.32 g of silver is
deposited in the silver
coulometer.
Answer: (a) 0.094g (b) 0.0355dm
3


(c) 17.8 cm
3


Figure 1
(a) Number of moles of silver deposited = 0.32/108 = 2.96 x 10
-3

mol
1F = 1mol e = 1 mol Ag = mol Cu
2+


Number of moles of Cu deposited = x 2.96 x 10
-3


= 1.48 x 10
-3

mol
Mass of Cu deposited = 1.48 x 10
-3

mol x 63.5 g/mol
= 0.094 g
(b) 1 F = Ag
+
= H
2

Number of moles of H
2
liberated = x 2.96 x 10
-3


= 1.48 x 10
-3

mol
Volume of H
2
liberated = 1.48 x 10
-3

mol x 24
= 0.0355 dm
3


(c) 2O
2-

O
2
+ 4e
Number of moles of O
2
liberated = x 2.96 x 10
-3


= 7.40 x 10
-4

mol
Volume of H
2
liberated = 7.40 x 10
-4

mol x 24 x 1000
= 17.8 cm
3


Miskonsepsi Pelajar 1
Anion sudah mencapai keadaan oktet; sudah
stabil, mengapa masih berlaku tindakbalas
pada anod sel elektrolisis?
Miskonsepsi: Anion stabil tetapi bersifat
nukleofilik (kaya elektron) dan juga reaktif; ia
gemar untuk mendermakan elektronnya bagi
membentuk kestabilan baru melalui ikatan
kovalen.
Miskonsepsi Pelajar 2
Kenapa dalam sel elektrolisis kation pergi ke
katod; tidak ke anod?
Jawapan: Kation bercas positif dan katod
bercas negatif. Cas +ve dan ve akan saling
tarik menarik.