Electrochemistry-I

Unit-I, Chapter-1
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ELECTRICAL TRANSPORT

ELECTROLYTIC AND METALLIC CONDUCTION:-

Substances which allow electricity to pass
through them are known as conductors whereas substances which do not allow electricity to pass
through are known as insulators. Conductors are divided into two classes:

(i) Those which conduct electricity without undergoing any decomposition. These are called electronic
conductors, e.g., metals, graphite and certain minerals. As the name indicates, the conduction in this
case is due to the flow of electrons.

(ii) Those which undergo decomposition when current is passed through them. These are known as
electrolytic conductors or electrolytes, e.g., solution of acids, bases and salts in water, fused salts etc. In
this case, the flow of electricity is due to the movement of ions.

Electrolytes are further classified into two main categories as strong electrolytes and
weak electrolytes.
Strong electrolytes are substances like strong acids, e.g., HCl, HNO3, H2SO4 etc.,
strong bases, e.g., NaOH and KOH etc., and most of the inorganic salts. These dissociate almost
completely in the aqueous solution or in the molten state and hence conduct electricity to a large
extent.
Weak electrolytes are substances like weak acids, e.g CH3COOH, HCN, H2CO3, H3PO4 etc. and
weak base, e.g., NH4OH, Ca(OH)2, Al(OH)3 etc. These have low degree of dissociation and hence conduct
electricity to a small extent.
Substances like sugar, urea etc. the solution of which do not conduct
electricity are known as non-electrolytes.

Factors affecting electrolytic conduction: -

The conductance of the solution of an electrolyte
depends upon the following factors: -

(i) Interionic attractions: -

Which depend upon the interactions between the ions of the solute and
hence are called solute-solute interactions.
On this basis, the substances are classified as strong
electrolytes and weak electrolytes, as already mentioned.
(ii) Solvation of ions: -
Which depends upon the interactions between the ions of the solute and
the molecules of the solvent and hence are called solute-solvent interactions.

(iii) Viscosity of the solvent: - Which depends upon the solvent-solvent interactions.
The effect of
all these factors decreases with increase of temperature. Hence, the electrolytic conduction increases
with increase of temperature. On the other hand, the electrical conduction of the electronic conductors
decreases with increase of temperature.
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Alternatively:-
The factors on which the electrolytic conduction depends are as follows: -

(i) Nature of the electrolyte: -

Strong electrolytes ionize almost completely in the solution and
hence conduct electricity to a large extent whereas weak electrolytes ionize to a small extent and hence
conduct electricity also to a small extent.

(ii) Nature of the solvent: -

Electrolytes ionize more in a polar solvent. Hence, greater is the
polarity of the solvent, greater is the ionization and hence greater is the conduction.

(iii) Concentration of the solution: -

Higher the concentration of the solution, less is the
conduction. This is because in a weak electrolyte, the ionization is less whereas in a strong electrolyte,
the interionic attractions are high at higher concentrations. With dilution, the conduction increases.

(iv)Temperature: -
On increasing the temperature, the dissociation increases and hence the
conduction increases.

Difference between metallic conductors and electrolytic conductors: -

The main points of
difference between metallic conductors and electrolytic conductors may be summed up in Table.

TABLE:- Difference between metallic conductors and electrolytic conductors

METALLIC CONDUCTORS ELECTROLYTIC CONDUCTORS

1. Flow of electricity takes place without the 1. Flow of electricity takes place accompanied by
decomposition of the substance. the decomposition of the substance (electrolyte).

2. Flow of electricity is due to the flow of electrons 2. Flow of electricity is due to the movement of
only, i.e., there is no flow of matter. The ions and hence there is flow of matter.
conductance depends upon the structure and
density of the metal and the number of valence
electrons per atom.

3. The electrical conduction decreases with 3. The electrical conduction increases with
increase of temperature. This is because kernels increase of temperature. This is generally due to
start vibrating which produce hindrance in the increase in dissociation or decrease in the
flow of electrons. interionic attractions.

4. The resistance offered by metal is also due to 4. The resistance shown by an electrolyte solution
vibrating kernels. is due to factors like interionic attractions, viscosity
of solvent etc.

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ELECTRICAL RESISTANCE AND CONDUCTANCE: - Every substance offers resistance to the flow of
electricity to a small or large extent. The law that gives the exact value of the resistance is known as
Ohm’s law. It states that:
If to the ends of a conductor is applied a voltage ‘E’ and a current ‘I’ flows through it,
and then the resistance ‘R’ of the conductor is E/I.

Current is generally measured in amperes, whereas voltage is

measured in volts. If one ampere current flow through a conductor when a voltage of one volt is applied
to it, the resistance of the conductor is taken as 1 ohm (written as 1 Ω).

Thus, according to Ohm’s law,

E Volts
R= or Ohms = Amperes
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In terms of SI base units, Ω = (kg m2)/(s3A3)

V Work per unit charge Work 1 FxI 1

This is explained below: Ω= = = x = x
A A Charge A Axs A

mxaxI kg x ms− x m kg m2
= = =
A2 s A2 s s3 A2

It is seen that like metallic conductors, solutions of all electrolytes also obey Ohm’s law.

It is obvious that a substance which offers greater resistance will allow less electricity to
flow through it. This result also follows from Ohm’s law according to which I ∝ I/R.

The reciprocal of the electrical resistance is called the conductance. It is usually represented by C. Thus

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C=
R

It is a common practice to speak o the conductance of a solution rather than its resistance.

Units: - The units of conductance are Siemens (S) or reciprocal ohms written as ohm— or mho or r.o.
(1S = 1 Ω—)
For example, if a solution has a resistance of 10 ohms, it is said to have a conductance of
1/10 ohm— or 1/10 mhos or 1/10 Ω—1 or 1/10 siemens.

SPECIFIC, EQUIVALENT AND MOLAR CONDUCTIVITIES: -

Specific conductivity (or simply called conductivity): -

It is observed that resistance R of a conductor is

(i) directlt proportional to its length (l) and

(ii) inversely proportional to its area of cross section (a)

l l
i.e., R∝ or R=𝜌a
a
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where 𝜌 is a constant of proportionality, called Specific Resistanve or Resistivity. Its value depends upon
the material of the conductor.

“The reciprocal of resistivity is known as specific conductivity or simply conductivity”. It is

denoted by k (kappa) or K. Thus, if K is the specific conductivity and C is the conductance of the solution,
then
1 1
R= and 𝜌=
C K

1 1 l
∴ = x
C K a

l
K=Cx
a

Now, if l = 1 cm and a = 1 sq. cm, then K = C. Hence,

Specific conductivity of a solution of 1 cm length and

having 1 sq. cm as the area of cross section. Alternatively, it may be defined as “conductance of one
centimeter cube of the solution of the electrolyte” fig. or in terms of SI base units, it is defined as the
conductance of 1 m3 of the conductor.

If the volume of the solution is V cm3, the

specific conductivity of such a solution at this dilution V is
written as Kv. Similarly, at concentration C, it is represented as
Kc.

a
Units: - Resistivity (𝜌) = R
l

(cm2 )
= ohms = ohm cm or Ω cm
cm

or Ω m in SI units

1 Ω m = 100 Ω cm

1
Specific conductivity (K) =
ρ

1
= = ohm—1 cm—1 or Ω—1 cm—1 or S cm—1
ohm cm

or S m—1 in terms of SI units.

1 S cm—1 = 100 S m—1

EQUIVALENT CONDUCTANCE: -
Equivalent conductivity of a solution at a dilution V is defined as the
conductance of all the ions produced from one gram equivalent of the electrolyte dissolved in V cm 3 of
the solution when the distance between the electrodes is one cm and the area of the electrodes is so
large that whole of the solution is contained between them. It is represented by 𝜆eq (lambda).
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RELATIONSHIP BETWEEN EQUIVALENT CONDUCTIVITY AND SPECIFIC CONDUCTIVITY:-
The equivalent conductivity of a solution is usually not found directly but is
calculated from the specific conductivity. The relationship between equivalent conductivity specific
conductivity may be obtained as follows:
Consider a rectangular vessel with its two opposite walls one cm apart and
made of some metal sheet so that these act as the electrodes.

Case I: -
Suppose 1 cm3 of the solution containing 1 g eq. of the electrolyte is taken in the vessel. The
conductance of this solution will be then its specific conductivity. Further, if 1 cm 3 of the solution taken
contains one gram equivalent of the electrolyte, the conductance of the solution will be its equivalent
conductivity (by definition). Thus, when 1 cm3 of the solution containing one gram equivalent of the
electrolyte is considered, the equivalent conductivity is equal to its specific conductivity.

Case II: -
Suppose 4 cm3 of the solution containing one gram equivalent of the electrolyte is taken.
The conductance of the solution will be still equal to its equivalent conductivity at this dilution but now
there will be four cubes each ob volume 1cm3 as shown in fig. The conductance of each 1 cm3 of the
solution is equal to its specific conductivity so that the total conductance of the solution, i.e., equivalent
conductivity is four times the specific conductivity.
In general, if the volume of the solution
containing one gram equivalent of the electrolyte is V cm3, we
have

Equivalent conductivity = Specific conductivity x V

𝝀eq = Kv x V
Figure
Relationship between equivalent conductivity
and specific conductivity.

In terms of concentration, if the solution has a concentration of c gram equivalent per litre, i.e.,
cgram equivalents are present in 1000 cm3 of the solution, then the volume of the solution containing
1000
one gram equivalent will be c . Hence, the above expression may be written as

𝟏𝟎𝟎𝟎 𝟏𝟎𝟎𝟎
𝝀eq = Kc x = Kc x 𝐍𝐨𝐫𝐦𝐚𝐥𝐢𝐭𝐲
𝐜𝐞𝐪

Note carefully that in the above expression, V is the volume of the solution in cm 3 containing 1
gram equivalent of the electrolyte and c is the concentration in gram equivalent/litre.

Units: - 𝜆eq = Kv x V

cm3
= ohms−1 cm−1 x Gram Eq

= ohm−1 cm2 (g eq)−1 or Ω−1 cm2 eq−1

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 or s cm2 eq−1 or s m2 eq−1 in SI units

1 s m2 eq−1 = 104 s cm2 eq−1

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If the volume of the solution is V cm3, the specific conductivity of such a solution at this dilution V is
written as Kv. Similarly, at concentration C, it is represented as Kc.

a
Units: - Resistivity (𝜌) = R
l

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Conductometric Titration: -
The titration in which the end point or equivalence point (of acid-alkali
reactions, some displacement reactions or precipitation reactions) is determined by means of
conductance measurement, are called Conductometric Titration.

Principle: -
The principle underlying in this method is that, the conductance of an electrolyte solution at
a particular temperature is due to the number of ions, their charges and their ionic mobilities. During
the process, there happens variation in conductance values due to change in concentration of particular
ions and also displacement of one ion by other having different ionic mobilities. At the end point, there
happens a sharp change in conductance value.

Thus, by noting down the conductance values during the course of titration and plotting the
data against the volume of titrant added, two linear curves are obtained. The end point is obtained by
extrapolating the two lines and then finding out their point of intersection. The Conductometric
titrations involving different reagents are described below:

(1) Titrations of a strong acid with a strong base: -

Let us consider strong acid as Hydrochloric acid (HCl)
and strong base as NaOH. A definite volume of strong acid solution is taken in a conductivity cell and the
strong base is added from a burette in definite amounts. After each addition, the value of conductance
is noted and the observed conductance is plotted against volume of NaOH added. When NaOH solution
comes in contact with HCl, the following reaction takes place.

HCl + H2O H+(aq) + Cl−(aq)

NaOH + H2O Na+(aq) + OH−(aq)

H+(aq) + Cl−(aq) + Na+(aq) + OH−(aq) Na+(aq) + Cl−(aq) + H2O(l)

From the above reaction, it is clear that H+ ions

of HCl combines with OH− ions of NaOH to give weakly
dissociated water. As NaOH solution addition continues,
the concentration of highly mobile H+ ions goes on
decreasing and those get replaced by comparatively less
mobile Na+ ions in the solution such a decrease in H+ ion
concentration decreases the conductance value. This
decreasing trend continues till the complete conversion
of H+ ions into water, i.e., up to neutralization point.

After the neutralization point, further addition

of NaOH solution results in sharp rise in conductance
value due to an increase in the concentration of fast moving OH− ions and accumulation of Na+ ions in
solution. Hence the conductance of such a system is minimum at the end point.

The line AB is due to consumption of fast moving H+ ions and curve (line) CD is due to
accumulation OH− and Na+ ions. The point of intersection of these two lines when these are
extrapolated, gives the end point (x).

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(2) Titration of a strong acid with a weak Base: -
Let us consider strong acid as HCl and weak base as
NH4OH solution. A define volume HCl solution is taken in a conductivity cell and NH4OH solution is
added from a burette in definite amount. When NH4OH solution comes in contact with HCl solution, the
following reaction takes place.

HCl + H2O H+(aq) + Cl−(aq)

NH4OH + H2O NH+4(aq) + OH−(aq)

H+(aq) + Cl−(aq) + NH+4(aq) + OH−(aq) NH+4(aq) + Cl−(aq) + H2O(l)

The conductance of HCl solution in absence of NH4OH is

very high due to fast moving H+ ions of HCl. As NH4OH
addition continues, the conductance value decreases due
to replacement of fast moving H+ ions by slow moving
NH4+ ions. The decreasing trend proceeds up to the end
point i.e., till the complete consumption of all the H+ ions.
After the end point, further addition of NH4OH solution
causes a very little or no change in the conductance value
because NH4OH being a weak base has very low degree of
ionization. Again the dissociation of NH4OH is suppressed
by NH+4 ions of NH4Cl by common ion effect.

From fig, the sharp curve AB is due

H+
to consumption of ions and the line CD is due to base
NH4+ and Cl− ions of NH4Cl.

(3) Titration of a weak acid against a strong base: -

Let us consider the weak acid as acetic acid
(CH3COOH) and the strong base as NaOH solution. A definite volume of weak acid (CH 3COOH) is taken in
the conductivity cell and NaOH solution is added from a burette in definite amounts. After each
addition, the value of conductance is noted and these values are plotted against the volume of NaOH
solution added. When NaOH solution comes in contact with CH3COOH solution the following reaction
takes place.
NaOH + H2O Na+(aq) + OH−(aq)

CH3COOH(aq) + Na+(aq) + OH−(aq) CH3COO−(aq) + Na+(aq) + H2O (l)

The conductance value of the CH3COOH

solution before the addition of NaOH solution, is low due to poor
dissociation of weak acid. As NaOH solution addition continues at
first there happens a decrease in conductance value due to
suppression of the dissociation of CH3COOH by highly dissociated
sodium acetate (i.e. , CH3COONa) molecules by common ion
effect. Then there happens a slow rise in the conductance value
due to the accumulation of Na+ and CH3COO− ions.

After attaining the end point, the

conductance value increases sharply due to fast moving OH− ions.
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(4) Titration of weak acid and weak Base: -
Let us consider the weak acid as acetic acid (CH3COOH) and
weak bases ammonium hydroxide (NH4OH). A definite volume of weak acid (CH3COOH) is taken in a
conductivity cell and weak base (NH4OH) solution is added to it from a burette in definite amounts. After
each addition, the conductance value is noted and these values are plotted against volume of NH 4OH
added. When NH4OH solution comes in contact with CH3COOH solution the following reaction takes
place.
CH3COOH(aq) + NH4OH(aq) CH3COO−(aq) + NH+4(aq) + H2O(l)

In such a case, before the addition of NH4OH solution, the

conductance value is lower due to weakly dissociated CH3COOH. As
NH4OH solution is added, the conductivity decreases, at first due to
depression of the dissociation of CH3COOH. Thereafter, the
conductance value increases slowly upto the end point due to the
accumulation of CH3COO− and NH4+ ions.

After the end point, CH3COONH4

(ammonium acetate) undergoes hydrolysis giving weakly dissociated
CH3COOH and NH4OH.

Some Advantages of Conductometric Titration: -

The process of Conductometric titration has a number
of advantages over ordinary titration. Some important advantages are:

1. The coloured solutions which cannot be titrated by using an indicator can be successfully titrated
Conductometrially.

2. The methodology does not require any special care at the end point because the end point is
determined graphically.

3. This methodoly is a very good technique for the titration of very dilute solutions.

4. Weak acids and weak bases can be titrated conductometrially.

5. No indicator is required in this titration.

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