Chapter 4

ELECTROCHEMISTRY
Lecture/Lession Plan -1

ELECTROCHEMISTRY

4.1 Concept of electrochemistry

Electrochemistry is a branch of chemistry where we will study how chemical energy can be trans-
formed into electrical energy and vice versa. Substances which conduct electricity or current are
termed as conductors. Metals and electrolytes are good conductor of electricity; metal carries cur-
rent by flow of electron where no matter is being transported during current flow whereas in case
of electrolytes, movement of ions (matter) is responsible for electricity flow. During current flow an
internal force of the conductor resist the flow of current through it which is known as resistance of
the conductor.

4.2 Conductance
According to Ohm’s law, resistance (R) of any conductor is directly proportional to its length (l)
and inversely proportional to its area of cross section (a). Ohm’s law can be expressed as:

l
R = ρ
a
; where is specific resistance or resistivity. When l=1 cm and a=1 cm2 then ρ will be equal to R.
Hence specific resistance or resistivity of a conductor can be defined as the resistance of the conduc-
tor having 1 cm length and 1 cm2 area of cross section.
Unit of resistance is ”ohm” and unit of specific resistance can be determined as:

l
R = ρ
a
l
or, ρ = R
a

7
8 CHAPTER 4. ELECTROCHEMISTRY LECTURE/LESSION PLAN -1

Unit of specific resistance

ohm.cm.cm
=
cm
= ohm.cm

Conductance (Λ) can be defined as reciprocal of resistance.

4.2.1 Specific conductance

specific conductance (κ) can be defined as reciprocal of specific resistance. Conductance is basi-
cally the ease of current flow through a liquid conductor. specific conducatance is defined by the
conductance of a solution of the dissolved electryle and the whole solution is being placed between
two electrode of 1 sq. cm area and 1 cm. Unit of conductance will simply be reciprocal of unit of
resistance i.e.,
1
= ohm−1 = mho.
ohm
Unit of specific conductance =
1
= mho.cm−1
ohm.cm

4.2.2 Equivalent conductance

Form the expression of conductance, we know that
1
Λ =
R
1a
=
ρl
1al
=
ρll
V
= κ 2;
l
where V = volume of the solution = area x length= a x l
Equivalent conductance is defined by the conductance of a solution containing 1 gm-equivalent of
the dissolved electrolyte and the whole solution is being placed between two electrode of 1 sq. cm
area and 1 cm apart.
Thus equivalent conductance

(Λ) = κV

(as l = 1 cm2 )
Now, say c gm-equivalent dissolved in 1000 cc of solution
So, 1 gm-equivalent will be present in
1000
cc solution.
c
4.2. CONDUCTANCE 9

So, equivalent conductance

1000κ
(Λ) =
c

Unit of equivalent conductance =

mho.cm−1 mho.cm−1
= = mho.cm2 .gm-equivalent−1
gm-equivalent.cc gm-equivalent.cm3

4.2.3 Molar conductance

Molar conductance is defined by the conductance of a solution containing 1 gm-mole of the dissolved
electrolyte and the whole solution is being placed between two electrode 1 cm apart.
Molar conductance
(Λm ) = κV
(V = volume of a solution containing 1 gm-mole dissolved electrolyte)
Now, say c gm-mole dissolved in 1000 cc of solution
So, 1 gm-mole will be present in
1000
cc solution.
c

So, equivalent conductance

1000κ
(Λ) =
c

Unit of equivalent conductance =

mho.cm−1 mho.cm−1
=
gm-mole.cc gm-mole.cm3
= mho.cm2 .gm-mole−1 .
Relation between equivalent conductance and molar conductance Let us consider an elec-
trolyte (molecular weight M) having weight W gm taken in between two electrode (in the cubic
core);p and q are the valency and number of cations are respectively.

M
Now, equivalent weight of the electrolyte is; E =
pq

W
C gm equivalent equivalent =
E
W
= m
pq
W × pq
=
M
10 CHAPTER 4. ELECTROCHEMISTRY LECTURE/LESSION PLAN -1

1000κ
Now, equivalent conductance = Λ=
c
1000κ
=
W×pq
M
1000κ
=
M gram mole × pq
Λm
=
pq
So,

Λm = Λ × pq

4.3 Effect of temperature on equivalent conductance

In general equivalent conductance should increase with temperature as with increased temperature,
the dissociation of electrolyte and ionic mobility of ions incresaes. Conductance and temperature
are corelated by this equation:

Λ0T = Λ0250 C [1 + α(T − 250 C]

; where Λ0T and Λ0 0 are the equivalent conductance at T0 C and 250 C respectively; α is the tem-
25 C
perature coefficient.

4.4 Effect of concentration on equivalent conductance

Conductance of an electrolyte depends on the number of ions present in the solution and the speed
of the ions which is known as ionic mobility. As strong electrolyte already completely dissociated in
solution hence number of ions do not changes with dilution. Therefore, the conductance of a strong
electrolyte depends upon only the ionic mobility of the ions present in solution. In a concentrated
solution, the density of ions are high as the the attraction between ions are high. According to Debye
and Huckel, at high concentration a particular type of ion is surrounded by the opposite charged ions
and thus a ionic cloud is being created. A cationic cloud formed on an anion and vice versa. These
ionic clouds are generally spherical when no electric fields is present. But in presence of an external
electrical field these ionic spheres get distorted. As the extend of ionic cloud distortion increases the
the ionic mobility decreases. This is commonly known as relaxation effect. As dilution increases,
the extend of this distortion decreases or the attraction between ions decreases; as a result the ionic
mobility or the conductance of the solution increases. With increase in concentration, the equivalent
conductance of any electrolyte decreases but the pattern of the graph is different for strong and
weak electrolyte. Conductance generally depends upon the number of ions and speed of ions (ionic
mobility).
Strong electrolytes are completely dissociated in solution and hence decrease in concentration or
increase in dilution will increase the ionic mobility only. Hence the with dilution equivalent conduc-
tance will increase slightly in a regular straight line. At infinite dilution this value will reach at its
maximum which is termed as limiting equivalent conductance (Λ0 ). Example of strong electrolytes
are NaCl, KCl, K2 SO4 ,HCl, H2 SO4 , HNO3 , NaOH, KOH etc.
4.4. EFFECT OF CONCENTRATION ON EQUIVALENT CONDUCTANCE 11

Equivalent conductance vs concentration for strong electrolyte

The relationship between concentration of any electrolyte and its equivalent conductance is given
by Debye-Huckel-Onsagar equation:
√
Λeqv. = Λ0 − b c;
where b is a constant and its value depends upon stoichiometry of the electrolyte of interest, c is
the concentration of the electrolyte in gm-eqv./L.
Weak electrolytes are partially dissociated in solution and hence with increase in dilution or decrease
in concentration both the dissociation of electrolytes and the number of ions increases. These two
combine effect increases equivalent conductance exponentially and becomes almost equal parrallel
to y-axis.

Equivalent conductance vs concentration for weak electrolyte

Thus at infinite dilution, the equivalent conductance of a weak electrolyte can not be determined.
But from Kohlrausch’s law, indirectly we can calculate that. So for weak electrolyte when equiva-
lent conductance reaches maximum at almost complete dissociation, i.e.; dissociation constant (α)
is close to unity. α can be expressed as a ratio of equivalent conductance at a certain concentration
of a electrolyte(Λ) with equivalent conductance at infinite dilution Λ0 of same electrolyte.
12 CHAPTER 4. ELECTROCHEMISTRY LECTURE/LESSION PLAN -1

4.5 Transport number and Ionic conductance

Transport number can be defined as fraction of current transported by a particular type of ion in a
solution of electrolyte.
So, transport number for cation
I+
t+ =
I
and transport number for aniion
I−
t− = ;
I
where I+ is the amount of current carried by cation and I− is the amount of current carried by
anion. Current carried by any type of ion depends upon speed of ions (u), charge of the ions (c) and
valency of ion (z). Thus
I+ ∝ u+ c+ z+
and
I− ∝ u− c− z−
Hence,
u + c+ z+
t+ =
(u+ c+ z+ ) + (u− c− z− )
and
u − c− z−
t− =
(u+ c+ z+ ) + (u− c− z− )
Thus,
u+
t+ =
(u+ ) + (u− )
and
u−
t− =
(u+ ) + (u− )
Let us consider at infinite dilution the ionic conductance of cation is λc and ionic conductance of
anion is λa . Now as ionic conductance varies directly proportional to speed of that particular type
of ion-
u+ ∝ λc and u− ∝ λa
Thus,
λc λa
t+ = and t− =
(λc + λa ) (λc + λa )
λc λa
or, t+ = and t− =
Λ0 Λ0
So, transport number of a particular type of ion can be expressed as fraction of conductance at
infinite dilution offered by that particular type of ion.
4.6. MOBILITY OF H+ AND OH− IONS IN AQUEOUS SOLUTION 13

Transport number by Hittroff’s method

4.6 Mobility of H+ and OH− ions in aqueous solution

The ionic mobility and hence the conductance value of both H+ and OH− ion is very high. The
conductance value of H+ and OH− ions are 350 mho.cm2 .mole−1 and 200 mho.cm2 .mole−1 respec-
tively.
Earlier it was considered that high charge density of both the ion is responsible for this abnormal
high conductance. But in aqueous solution the H+ ion basically exists as a hydroxonium ion H3 O+ .
The high mobility can be explained by the fact that from hydroxonium ion the H+ ion migrates
to neighboring water molecule and thus the proton molecule is transported from one molecule to
other molecule of water. Thus in presence of an external field water molecule migrates from one
molecule to another molecule. A proton does not travel an entire distance up to the electrode rather
it only travels the distance between two water molecule. This mechanism is known as Grotthus-type
mechanism.
Hydroxyl ion are getting transported in similar manner. The major difference is that in proton
transfer proton transported from hydroxonium ion to water molecule but in case for hydroxide ion
transport proton transported from water to adjacent hydroxide ion.