Electrolysis

Electrolysis
Process by which an electric current is

passed through a substance to cause a

chemical change.
The chemical change is one in which the
substance loses or gains an electron.

Electrolysis
The process uses an apparatus consisting of positive

and negative electrodes which are separated from

each other in a solution.
Electric current enters through the negatively
charged electrode (cathode).
Positively charged parts of the solution travel to the
cathode, combine with the electrons, and are
transformed into neutral molecules.
The negatively charged parts of the solution travel
to the positive electrode (anode), give up electrons,
and are transformed into neutral molecules.

Diagram of Electrolysis

Electrolysis Apparatus

Electrolysis of Water
Water is split with electricity to

produce hydrogen gas and oxygen

gas.

Electrolysis of Water

Electrolysis of Copper
Chloride
Copper chloride is split with an electrical

current to produce copper and chlorine gas.

During electrolysis, copper loses electrons,
has an overall positive charge, and becomes
a cation, which is attracted to the cathode
or negative electrode.
Chlorine gains electrons, has an overall
negative charge, and becomes an anion,
which is attracted to the anode or positive
electrode.

Electrolysis of Copper
Chloride

OHMS LAW

VOLTAGE (V)
I It is the push or pressure behind

current flow through a circuit, and

is measured in (V) volts. t is the
push or pressure behind current
flow through a circuit, and is
measured in (V) volts.

CURRENT
tCurrent refers to the
quantity/volume of electrical
flow. Measured in Amps (A)
ity/volume of electrical flow.
Measured in Amps (A)

RESISTANCE
Resistance

to the flow of the

current. Measured in Ohms
stance to the flow of the
current. Measured in Ohms

Chart

How do we used Ohms

law

(E) = I x R

=V
R

R=V
I
V (E) = I x R
I = V

R
R=V
I

Faradays law
If W grams of the substance is deposited by
Q coulombs of electricity, then

W Q
But Q = it, Hence W

it

or W = Z it
I = current in amperes
t = time in seconds.
Z = constant of proportionality
(electrochemical equivalent.)

Faradays Law
By definition Z

E
96500
I.t.E
96500

E=Equivalent mass of the substance

1 Faraday=96500 coulomb

Na e
1F

23 g

Al3 3e
3F

Al
27g

9g

Cu2 2e
2F

Cu E
63.5 g

Na
23g

31.75 g

Faradays second law

of electrolysis

When the same quantity of electricity is passed through different

electrolytes the masses of different ions liberated at the electrodes are
directly proportional to their chemical equivalence

W1 E1
Z It E

or 1 1
W2 E2
Z2It E2
Z
E
Hence, 1 1
Z2 E2

Resistance
Resistance refers to the opposition
to the flow of current.
For a conductor of uniform cross section(a)
and length(l); Resistance R,

l
R l and R
a

l
R
a

a
Where is called resistivity or
specific resistance.

Conductance
The reciprocal of the resistance is
called conductance. It is denoted by C.
C=1/R
Conductors allows electric current to pass through
them. Examples are metals, aqueous solution of
acids, bases and salts etc.
Unit of conductance is ohm-1 or mho or Siemen(S)
Insulators do not allow the electric current to
pass through them.
Examples are pure water, urea, sugar etc.

Specific Conductivity
Specific conductance

Conductance of unit volume of

cell is specific conductance.

But =

a
R
l

l
a.R

l
K x Conductance
a

l/a is known as cell constant

Unit of specific conductance is ohm1cm1
SI Unit of specific conductance is Sm1 where S is Siemen

Equivalent
Conductance
It is the conductance of one gram
equivalent of the electrolyte dissolved
in V cc of the solution.

Equivalent conductance is represented

by Mathematically,
k V
k

1000
Normality

Where,
k = Specific conductivity
V = Volume of solution in cc. containing one gram equivalent
of the electrolyte.

Molar conductance
It is the conductance of a solution containing 1
mole of the electrolyte in V cc of solution. it is
represented as .
=kV
=k x 1000/M
Where V = volume solution in cc
Molar conductance
k = Specific conductance
M=molarity of the solution.

Relation between equivalent

conductivity and molar conductivity
= valency factor(or n - factor)
i.e.
Molar conductivity = n- factor x equivalent conductivity

Measurement of conductance

conductivity
cell

Type 206
conductance electrode

Wheatstone
Bridge
Circuit

High-frequency alternative current,

frequency = 1000 Hertz

R1 / R 2 = R 3 / R 4

R2 R3
R1
R4

Cell constant
of a
conductivity
l
cell

1
G
R1

K cell G

K cell R

K cell R1 R1 x Rx
The conductance cell is usually
calibrated with standard KCl
(potassium chloride ) solution.
C/ mol dm-3 0
0.001
0.01
0.1

/ S m-1

0.0147 0.1411 1.289

1.0
11.2

Influential factors for

conductivity
1) Concentration.
2)

Type of electrolyte

3)

Temperature

1. Acids and bases

have higher
conductance
2. C < 5 mol dm-3,
increases with C
3. For CH3COOH
conductance does
not depend on C

(2)
Temperaturedependence
of
conductance

Dependence of molar
conductivity on
concentration
m decreases with
concentration.
Due to the
interaction
between ions:
interionic
Kohlrausch
attraction
replotted m
1/2

 m / Smol-1m2

0.04
HCl
0.03

H2SO4

0.02

KCl
Na2SO4

0.01
HAc
0.00

0.05

0.10

0.15
0.20
c / mol dm 3

Linear
relationship
between m
and C1/2 can
be observed
for 1:1
electrolytes:
C < 0.002~
0.003 mol dm3

Kohlrausch empirical formula

m A c
To extrapolate the linear part of m
~ C1/2 at low concentration to C =
0, m can be obtained.
m the limiting value of m at
infinite dilution: limiting molar
conductivity. It is the conductivity of
1 mol of solution at infinite dilution.

Kohlrauschs Law
Limiting molar conductivity of an electrolyte can be
represented as the sum of the individual contributions of
the anion and cation of the electrolyte.

a c
Where a and c
are known as ionic
conductance of anion and cation at
infinite dilution respectively.

Application of Kohlrauschs law

). It is used for determination of degree of

dissociation of a weak electrolyte.

Where,

represents equivalent conductivity at infinite dilution.

represents equivalent conductivity at dilution v.

(2). For obtaining the equivalent conductivities of weak

electrolytes at infinite dilution.

m ,

m ,

m v m, v m,

mm at
at infinite
infinite dilution
dilution isis made
made up
up of
of independent
independent
contributions
contributionsfrom
fromthe
thecationic
cationicand
andanionic
anionicspecies.
species.
Explanation to the same difference

m (KCl) m (NaCl) m,K + m,Cl- m,Na + m,Cl m,K + m,Na +

m (KNO3 ) m (NaNO3 ) m,K

m,NO
m,Na
m,NO
3

m,K

m,Na

4) Kohlrauschs law of independent migration

Salts

m/S mol-1 cm2

m

KCl

NaCl

KNO3

NaNO3

149.85

126.45

144.96

121.56

23.4

23.4

The difference in mof the two electrolytes containing the same

cation or anion is the same. The same differences in m led

Kohlrausch to postulate that molar conductivity at infinite
dilution can be broken down into two contributions by the ions.

m, /

m,

m,

ionic conductivities at infinite dilution

KOHLRAUSCHS LAW

How can we determine the limiting molar conductivity of

weak electrolyte

m (HAc) m (H ) m (Ac )
m (H ) m (Cl ) m (Na ) m (Ac ) m (Na ) m (Cl )

m (HCl) m (NaAc) m (NaCl)

m (HAc) (426.16 91.00 126.45)S m -1 mol -1

390.71S m -1 mol-1

m ,

m ,

Key:
Key:
How
Howto
tomeasure
measurethe
theionic
ionicconductivity
conductivityat
atinfinite
infinite
dilution?
dilution?

measurement of limiting molar conductivity of

1) Ionic mobility

dE

dl

dE
U
dl

Ionic velocity

Ionic mobility (U) : the ionic velocity per unit electric field, is a constant.
B
A
C
For time t:
Q+ = A U+t C+ Z+ F
Q = A Ut C Z F

C,Z,U;C,Z,
U ;

For time t:
Q+ = A U+t C+ Z+ F

Q = A Ut C Z F

I+ = AU+Z+c+F

I = AUZ c F

I = I++ I = Ac+Z+F(U++ U)

Ac Z F (U U )
G
V

l Ac Z F (U U ) l
G
A
V
A
c Z F (U U )

c Z F (U U )
V
l

c
Z
F
(
U

)
m
c

c
Z
F
(
U

)
m
c

For uni-univalent
electrolyte:

m m , m ,

m F (U U )

m,

U F

m,

U F

m ,
U F

m
(U U ) F

U
t
U U

m , t m

U
t
U U

m , t m

To measure m,+ or m,-, either t+ and t- or U+ and U- must be

determined.

( c) Mechanism of hydrogen and

hydroxyl ions transfer

Grotthus mechanism
(1805)

Applications of conductance measurment:

1)Determination of the solubility of a sparingly soluble salt:

The solubility of a sparingly soluble salt in a

solvent is quite low. Even a saturated solution of

such a salt is so dilute that it can be assumed to
be at infinite dilution. Then, the molar
conductivity of a sparingly soluble salt at infinite
dilution can be obtained from the relationship,
The conductivity of the saturated solution of the

sparingly soluble salt is measured. From this, the

conductivity of the salt can be obtained by using
the relationship,

where,

is the conductivity of the water

used in the preparation of the saturated
solution of the salt.
From equation (i) and (ii)

is the molar concentration of the sparingly soluble salt in its saturated solution and
is equal to the solubility of the sparingly soluble salt in the
mole per litre unit

2) Ostwalds Law of dilution :

Ostwalds dilution law is a relationship between the

dissociation constant and the degree of dissociation of a

weak electrolyte (acids, bases)

But concentration C = 1/v

for a weak electrolyteais very small ( and the law does not
apply to strong electrolytes)
K =a2C
For a weak acid =
and a weak base =

2) Transference
number
I = I+ + I Q = Q+ + Q-

tj

Qj
Q

The fraction of the current

transported by an ion is its
transference number or transport
number t = t + t
+

2) transference number or Transport number:

m , t m

m , t m

Transference number
I=I +I
Q=Q +Q

tj

Qj
Q

t = t+ + t- = 1

The fraction of the current transported by an ion is its

transference number or transport number
How to measure ionic mobility and transference number?

Measure transference number: 1)Hittorfmethod

Johann Wilhelm Hittorf

Cock stopper

Anode chamber

Cathode chamber

Hittorfs transference cell

(2) The moving-boundary method

MA, MA have an ion in common.
The boundary, rather different in
color, refractivity, etc. is sharp.
In the steady state, the two ions move with
the same velocity.
When Q coulomb passes, the boundary
moves x, the cross-sectional area of the
tube is A, then:
xAcZ+F = t+Q

Measurement of transference
numbers
1) Hittorf method (1853)

Electrolysis of HCl solution

Anodic
region

Bulk
solution

cathodic
region

When 4 Faraday pass through the

electrolytic cell

4 Cl- -4e- 2
Cl2
3 mol
H+ 1
mol Cl-

4 H+ +4e- 2
H2
3 mol
H+ 1
mol Cl-

For anodic
region:
C
=C
residual

initial

Creact + C

transfer

3) Relation between ionic mobility and

transference number

C-, Z-, u-; C+, Z+, u+;

For time t:

Q+ = A Eu+ t C+ Z+ F
Q = A Eut C Z F

Q = Q+ + Q = AtF E( u+C+ Z+ +
u C Z)

C+ Z+ = C Z

Q = AtF C+ Z+ E( u+ + u)

u
t
u u

u
t
u u

Relation between
transference number and
molar conductivity
I+ = AEu+Z+C+F
I =
AEuZ C F

I = I++ I = AC+Z+F E(u+

+ u )

AC Z FE (u u )
G
V

l AC Z FE (u u ) l
G
A
V
A
C Z FE (u u ) C Z FE (u u

V
E
l
C Z F (u u )


m
C

C Z F (u u )

C

For uni-univalent
electrolyte:

zF (u u )

u F

u F

u F

t

(u u ) F

To measure m+ or m- , either t+
and t- or u+ and u- must be
determined