CMT552

ELECTROCHEMISTRY AND
CORROSION SCIENCE
What is electrolyte?
Any substance that produce ions when
dissolved in a solvent (usually water) is an
electrolyte.
It is the electrically conductive solution that
must be present for corrosion to occur.
Types of electrolytes
Strong electrolyte
Weak electrolyte
Non-electrolyte
Strong
Electrolytes
Strong electrolytes are substances that only
exist as ions in solution.
They completely dissociate to their ions
when dissolved in solution.
Ionic compounds are typically strong
electrolytes.
Strong acids, strong bases and salts are
strong electrolytes.
They conduct electricity when molten or in
aqueous solution.
Example: Hydrochloric acid, Sodium chloride

+
+ + Cl Na O H NaCl
2
+
+ + Cl O H O H HCl
3 2
Weak
Electrolytes
A weak electrolyte only partially
dissociates in solution and produces
relatively few ions (exist in water as a
mixture of individual ions and incontact
molecules).
Polar covalent compounds are typically weak
electrolytes.
Weak acids and weak bases are weak
electrolytes.
They conduct electricity weakly.
Example: Acetic acid, ammonia
+
+ + H COO CH O H COOH CH
3 2 3

+
+ + OH NH O H NH
4 2 3
Non-
electrolytes
A non-electrolyte does not dissociate at all
(present entirely as intact molecules) in
solution and therefore does not produce any
ions.
Non-electrolytes are typically polar covalent
substances that do dissolve in water as
molecules instead of ions.
They do not conduct electricity at all.
Example: Sugar


11 22 12 2 11 22 12
O H C O H O H C +
Acids
Are molecular compounds which ionize or
turn into ions in water.
The properties of acids were due to the
presence of hydrogen ions, H
+
.
All acids are soluble in water
Some acids are strong electrolytes and
some are weak electrolytes.
No acids are non-electrolytes.
Bases
Can be molecular compounds or ionic
compounds.
Some bases are soluble and some are not.
The soluble bases ionize or dissociate into
ions in water.
The properties of bases were due to the
presence of hydroxide ions, OH
-
.
All of the ionic bases which are soluble are
also strong electrolytes.
Salts
Are ionic compounds which are not acids or
bases.
In other words, the cation is not hydrogen
and the anion is not hydroxide.
Some salts are soluble in water and some
are not.
All of the salts which are soluble are also
strong electrolytes.
Electricals
Terms
SI Term SI
Symbol
SI Unit
Electrical Current I Ampere (A)
Quantity of Electricity Q Coulomb (C)
Electric Potential V Volt(V)
Electric Resistance R Ohm(O)
Resistivity Om

Conductance G Siemens (S);ohm
-1
Conductivity k Sm
-1
; O
-1
m
-1
; O
-1
cm
-1

Molar conductivity A Sm
2
mol
-1

Molar Conductivity of Ion Sm
2
mol
-1

Electric Mobility of Ion u m
2
V
-1
s
-1
Transport Number of Ion t
Other Symbols and Terms
Symbol Term
C Molar Concentration, mol dm
-3
(with A:mol m
-3
)
o Degree of dissociation
l Length
A Area
K
cell
Cell Constant
A Molar conductivity at infinite dilution or Limiting
Molar Conductivity
Electrolytic conductance
Electrolytic conductance occurs when a
voltage is applied to the electrode dipped into
an electrolyte solution, ions of the electrolyte
move and electric current flows through the
electrolytic solution.
This power of the electrolyte to conduct
electricity is known as conductance or
conductivity.
Electrolytic solution also obey Ohms Law just
like metallic conductor.
Ohms Law: It states that the current flowing
through a conductor is directly proportional to
the potential difference across it:


where,
V = applied potential (V)
I = current measured (A)
R = solution resistance (O) between the two
electrodes
V=I
R
Solution Resistance
(R)
The increase the [ions] presence in the
solution, the lower the solution resistance,
R, will be.
A strong electrolyte like KCl is dissolve in
water, the no. of ions per unit volume
increase and the solution resistance, R, is
lowered, thus increasing the current
measured for a particular applied potential.
Thus, current can be related to the [ions] in
a particular solution.
However,
the distance between the electrodes,
the surface area of the electrodes and
the identity of the ions
also affect the solution resistance, R.
Solution Conductance
(G)
The reciprocal of solution resistance (1/R) is
called Conductance, G.
Conductance is expressed as Siemens (S)
or ohm
-1
(O
-1
) or mho.


Where, A = surface area of each electrode
l = distance btwn electrode
k = conductivity
l
A
R
G
k
= =
1
Values of conductivity,k, increased with T
and concentration.

The conductivity of a solution of water is
highly dependent on its concentration of
dissolved salts and sometimes other chemical
species which tend to ionize in the solution.



Electrical conductivity of water samples is
used as an indicator of how salt free or
impurity free the sample is; the purer the
water, the lower the conductivity.
Solution Electric Conductivity
(Sm
-1
)
Seawater 5
Drinking water 0.0005 to 0.05
Deionized water 5.5 x 10
-6
Molar Conductivity
(A)
Defined by:

Example 1:
Molar conductivity of 0.005 M KCl is 144 Scm
2
mol
-1
. Calculate its electrolytic conductivity in SI
units (Sm
-1
).

*(Hint: 1m
2
= 10
4
cm
2
; mol/L or mol/dm
3
convert to
mol m
-3
).

C
k
= A
Units: Sm
-1
mol m
-3
1 -
3
3 1
3
3
1 2
2 4
2
1 2
Sm 0.072
5 0.0144
m mol 5
m) 10 (1
dm 1
dm
mol 0.005
mol Sm 0.144
cm 10
m 1
mol Scm 144
=
=
A =
=

c k
Measurement of
Conductivity
The conductivity of a solution is measured in
a cell called conductance cell or conductivity
cell.



Since l and A are difficult to measure, the
usual procedure is to treat as a cell
constant, K
cell


|
.
|

\
|
=
A
l
R
1
k
A
l
Therefore,



Example 2
In a certain conductivity cell, the resistance
of a 0.01 M KCl solution is 150 O. The known
molar conductivity of the solution is 141.27 O
-
1
cm
2
mol
-1
. Calculate the cell constant (K
cell
).
*(K
cell
unit is cm
-1
)
( )
cell cell
GK K
R
= =
1
k
1
3
2119 . 0
10 150 01 . 0 27 . 141

=
=
A =
=
cm
cR
R k
cell
k

Exercise 1
Using the same conductance cell as in
example 2, a student measured the
resistance of a 0.10 M NaCl solution to be
19.9 O. Calculate the experimental value of
the molar conductivity of this solution.


Use the same value of k
cell

1 2
3
48 . 106
10 106485 . 0
9 . 19 1 . 0 2119 . 0

=
= A
A =
A =
=
mol Scm
cR
R k
cell
k
Ex
In order to determine the molar
conductivity of a 0.05 M solution of
AgNO
3
, you need to measure the
solution resistance in a conductivity cell
and found that R = 75.8 O. Then, in the
same cell, a 0.02 M KCl solution had a
resistance of 157.9 O. Given that the
accepted molar conductivity of the KCl
solution is 0.013834 O
-1
m
2
mol
-1
,
calculate the molar conductivity of the
AgNO
3
solution.
1 2
1 2 3 -
1 -
cell 3
1 -
3 -
cell
mol Sm 0.01153
mol Sm 10 11.53
75.8 0.05 m 43.7
cR k : AgNO
m 43.7
10 157.9 02 . 0 013834 . 0
k : KCl

=
=
=
=
=
=
A = cR
Variation of Molar Conductivity
with Concentration
Molar conductivity (A) of electrolytes
increases with dilution.
The variation is different for strong and weak
electrolytes.

Strong electrolytes
Fully ionized in solution
A increases slowly with dilution and there is
a tendency for A to approach a certain
limiting value when the concentration
approaches zero(i.e. When dilution is
infinite).

The A when the concentration approaches
zero (infinite dilution) is called molar
conductivity at finite dilution or limiting
molar conductivity (A).
A = A
when C 0 (at infinite dilution)

For strong electrolytes molar conductivity
increase slowly with dilution and can be
represented by:


C | A = A

DEBYE HUCKEL
ONSAGER equation
A = Molar conductivity at a given
concentration
A = Molar conductivity at infinite dilution
| = constant


C | A = A

From the graph, it has been noted that the
variation of molar conductivity (A) with
concentration (\C) is small so that the plot
can be extrapolated to zero concentration.
The intercept is equal to (A) and the slope is
-|.
b) Weak electrolytes
Not fully ionized in solution
In weak electrolyte like acetic acid they
have low degree of dissociation as
compared to strong electrolyte.
However, the variation of molar conductivity
(A) with concentration (\C) is very large and
we cant obtain molar conductivity at infinite
dilution (A) by extrapolation of A versus \C
plots. Explanation for the variation of
Molar Conductivity with
concentration
1. Conductance behaviour of strong
electrolyte:
No increase in the no. of the ions with the
dilution ( completely ionized in the solution at
all concentration).
In concentrated solution:
strong inter-ionic forces
Molar conductivity is low
In dilute solution:
Inter-ionic forces low
Molar conductivity increases with dilution

When concentration very low, inter-ionic
interaction becomes almost negligible and
molar conductance approaches the
limiting value, A.


2. Conductance behaviour of weak
electrolyte:
The no. of ions produced in solution
depends upon the degree of dissociation
with dilution.
Higher the degree of dissociation, larger is
the molar conductance.
With increase in dilution
Degree of dissociation increases as a
result molar conductivity increases.
At infinite dilution, the electrolyte is
completely dissociated so that the degree
of dissociation become one.

A
A
= o
Thus, if
A = Molar conductivity at a given
concentration
A = Limiting molar conductivity or molar
conductivity at infinite dilution
Then, degree of dissociation




A = A (at C 0)
Consider an aqueous solution of a
weak binary electrolyte, AB, of
concentration C mol dm
-3
and degree of
dissociation of o.




At equilibrium:

Ostwald Dilution Law &
Dissociation Constant of Weak
Electrolyte
AB (aq) A
+
(aq) + B
-
(aq)
Initial/mol dm
-3
C 0 0
Equilibrium/mol dm
-3
C(1-o) Co Co
] [
] ][ [
AB
B A
K
+
=
) 1 (
) )( (
o
o o

=
C
C C
K
c
o
o

=
1
2
C
K
c
Therefore, the dissociation constant
can be expressed as:
Ostwald Dilution
Law
However, for weak electrolyte; o is very
small.
Hence, (1- o) ~ 1
Therefore,




Since H
+
= Co
[H
+
] = Co =





2
o C K
a
=
C K H
C
K
C
a
a
=
+
] [
C
K
a
= o
KOHLRAUSCHS LAW
At infinite dilution the ions act completely
independently, and the A obeys a rule of
additivity:



where AX, AY, BX and BY are strong
electrolytes.
( ) ( ) ( ) ( ) BY BX AY AX

A A + A = A
A for a weak electrolyte can be deduced
from A values obtained from strong
electrolytes.
For example, consider CH
3
COOH denoted as
HAc:



where HX, Mac and MX are strong electrolytes.
( ) ( ) ( ) ( ) MX MAc HX HAc

A A + A = A
Table 1: Limiting Molar
Conductivity, A, of some strong
electrolytes
Electrolyte A (S cm
2
mol
-1
)
HCl 426.16
HBr 428.10
NaCl 126.45
KBr 151.80
KCl 149.86
NaNO
3
121.55
KNO
3
144.96
NH
4
Cl 149.70
KHCO
3
118.00
Exercise 2
Calculate A for a weak electrolyte NH
4
OH
from the A values for these strong
electrolytes: NH
4
Cl: 149.7; NaCl: 126.5 and
NaOH: 248.10


3 . 271
5 . 126 10 . 248 7 . 149
) ( ) ( ) ( ) (
4 4
=
+ =
A A + A = A NaCl NaOH Cl NH OH NH
Kohlrausch also stated at infinite dilution
when the dissociation complete,
each ion makes a definite contribution towards
molar conductance of the electrolyte
irrespective of the nature of the other ion with
which it is associated.


It means that the molar conductivity at
infinite dilution for a given salt can be
expressed as the sum of the individual
contributions from the ions of the
electrolyte.

where
v
+
and v
-
: stoichiometric coefficients for the
cation and anion in the electrolyte.

+
and
-
: ionic conductance of individual
ions (cation and anion)
+
+
+ = A

v v
Example 3
For NH
4
OH electrolyte: v
+
= 1 and v
-
= 1
Since 1NH
4
+
ion present for each OH
-
ion
present
in solution.

Example 4
For K
4
Fe(CN)
6
electrolyte: v
+
= 4 and v
-
= 1
Since there are 4K+ ions present for each
Fe(CN)
4-
6
ion present in solution.
Thus, the limiting ionic conductivities
represent the contributions to the total
solution conductivity made per mole of each
ion present in a dilute solution.

Exercise 3
Calculate the A of the following electrolytes:
1) Acetic acid
2) Hydrochloric acid
3) Potassium Chloride
Ionic Conductivities at Infinite
Dilution at 25C
Cation
+
/ Scm
2
mol
-1
Anion
-
/ Scm
2
mol
-1
H
+
349.6 OH
-
197.8
Li
+
38.7 Cl
-
76.4
Na
+
50.1 Br
-
78.2
K
+
73.5 I
-
76.8
Fe
2+
108.0 CH
3
COO
-

40.9
Fe
3+
204 CO
2-
3
138.6
NH
4
+
73.4 NO
-
3
71.5
Ba
2+
127.3 SO
2-
4
160.0

1 2
3
5 . 390
) 9 . 40 ( 1 ) 6 . 349 ( 1
) (

+
=
+ =
+ = A
+
mol Scm
v v COOH CH


Example 5
Molar conductivity for 0.10 M NaCl is 107 Scm
2

mol
-1
. Calculate the degree of dissociation for
the
Solution.

1) Calculate the limiting molar conductivity for
NaCl
2) Use formula

A
A
= o
846 . 0
5 . 126
107

5 . 126
) 4 . 76 ( 1 ) 1 . 50 ( 1
) (
=
=
A
A
=
=
+ =
+ = A
+ +
o
v v NaCl
Exercise 4
At 25 C, k = 3.40 10
-3
Sm
-1
for 0.001 M
NH
4
OH. Values of A are NH
4
Cl = 0.01497,
NaOH = 0.02481, NaCl = 0.01265 Sm
2
mol
-1
.
Calculate the dissociation constant, K, of
ammonium hydroxide.
1253 . 0
02713 . 0
10 40 . 3
10 40 . 3 10
001 . 0
10 40 . 3
02713 . 0
01265 . 0 02481 . 0 01497 . 0
) ( ) ( ) ( ) (
3
3 3
3
4 4
=

=
A
A
=
=

=
= A
=
+ =
A A + A = A

o
k
c
NaCl NaOH Cl NH OH NH