CHAPTER 3: ELECTROLYTIC CONDUCTANCE

3.1. Specific conductance

Specific conductance is a measure of the electric current in the water sampled
carried by the ionized substances, therefore the dissolved solids are basically related to this
measure that is also influenced by the good conductivity of inorganic acids, bases and salts
the poor conductivity  
characteristics of organic compounds.
1

It is the reciprocal of specific resistance.  (3.1)
It is the conductance of a solution of 1 cm length having 1 square cm as area of cross
section. It is defined as the conductance of a 1m cube of the solution.

l
R
Where specific resistance relates to resistance: A (3.2)
And A is the area of cross section of the conductor; l is the length of conductor
1 l

Eq (3.1) becomes R A (3.3)
1 1 1
Units: Ohm  cm  or S/cm
The ratio of l/A is known as the cell constant (k) and it is not easy to find from the
geometrical dimensions of the cell. Its value is calculated by measuring the conductance of
KCl(aq) solution of known specific conductance.
3.2. Molar Conductivity or Molar Conductance
Molar conductivity is defined as the conducting power of all the ions produced by
dissolving one mole of an electrolyte in solution.
It is denoted by  (lambda). Molar conductance is related to specific conductance (  ) as,


M where, M is the molar concentration.
If M is in the units of molarity i.e., moles per litre (mol.L 1) the  may be expressed as,
1000

M
Units of Molar Conductance?
3.3. Equivalent Conductivity
It is defined as the conducting power of all the ions produced by dissolving one gram
equivalent of an electrolyte in solution.
1000
e 
It is expressed as e and is related to specific conductance as N
where N is the concentration in gram equivalent per litre (or Normality). This term has
earlier been quite frequently used. Now it is replaced by molar conductance. The units of
equivalent conductance are Ohm1.cm2.(gm equiv)1 
3.4. Factors Affecting the Electrolytic Conductance
In general, conductance of an electrolyte depends upon the following factors,
+ Nature of electrolyte: The conductance of an electrolyte depends upon the number of
ions present in the solution. Therefore, the greater the number of ions in the solution the
greater is the conductance. The number of ions produced by an electrolyte depends upon
its nature. The strong electrolytes dissociate almost completely into ions in solutions and,
therefore, their solutions have high conductance. On the other hand, weak electrolytes,
dissociate to only small extents and give lesser number of ions. Therefore, the solutions of
weak electrolytes have low conductance.
+ Concentration of the solution: The molar conductance of electrolytic solution varies with
the concentration of the electrolyte. In general, the molar conductance of an electrolyte
increases with decrease in concentration or increase in dilution.
The molar conductance of strong electrolyte (HCl, KCl, KNO 3) as well as weak electrolytes
(CH3COOH, NH3) increase with decrease in concentration or increase in dilution. The
variation is however different for strong and weak electrolytes.
The variation of molar conductance with concentration can be explained on the basis of
conducting ability of ions for weak and strong electrolytes.
* For weak electrolytes the variation of  with dilution can be explained on the bases
of number of ions in solution. The number of ions furnished by an electrolyte in solution
depends upon the degree of dissociation with dilution. With the increase in dilution, the
degree of dissociation increases and as a result molar conductance increases. The limiting
value of molar conductance 0 corresponds to degree of dissociation equal to 1 i.e., the
whole of the electrolyte dissociates.
m

Thus, the degree of dissociation can be calculated at any concentration as, m0
where α is the degree of dissociation,
m is the molar conductance at concentration M and
m0  is the molar conductance at infinite dilution.
* For strong electrolytes, there is no increase in the number of ions with dilution
because strong electrolytes are completely ionised in solution at all concentrations (By
definition). However, in concentrated solutions of strong electrolytes there are strong forces
of attraction between the ions of opposite charges called inter-ionic forces. Due to these
inter-ionic forces the conducting ability of the ions is less in concentrated solutions. With
dilution, the ions become far apart from one another and inter-ionic forces decrease. As a
result, molar conductivity increases with dilution. When the concentration of the solution
becomes very-very low, the inter-ionic attractions become negligible and the molar
conductance approaches the limiting value called molar conductance at infinite dilution.
This value is characteristic of each electrolyte.
+ Temperature: The conductivity of an electrolyte depends upon the temperature. With
increase in temperature, the conductivity of an electrolyte increases.
 + Migration of ions
Electricity is carried out through the solution of an electrolyte by migration of ions.
Therefore,
(1) Ions move toward oppositely charged electrodes at different speeds.
(2) During electrolysis, ions are discharged or liberated in equivalent amounts at the two
electrodes, no matter what their relative speed is.
(3) Concentration of the electrolyte changes around the electrode due to difference in the
speed of the ions.
(4) Loss of concentration around any electrode is proportional to the speed of the ion that
moves away from the electrode, so

The relation is valid only when the discharged ions do not react with atoms of the
electrodes. But when the ions combine with the material of the electrode, the concentration
around the electrode shows an increase.
3.5. Ionic migration
Remember: The thermally-induced random motions of molecules is known as diffusion.
The term migration refers specifically to the movement of ions due to an externally-applied
electrostatic field.
All ionic solutions contain at least two kinds of ions (a cation and an anion), but may
contain others as well. In the late 1870's, the physicist Friedrich Kohlrausch noticed that the
limiting equivalent conductivities of salts that share a common ion exhibit constant
differences.
electrolyte e0 (25 C) difference electrolyte e0 (25 C) difference
KCl 149.9 34.9 HCl 426.2 4.9
LiCl 115.0 HNO3 421.1
KNO3 145.0 34.9 LiCl 115.0 4.9
LiNO3 110.1 LiNO3 110.1
These differences represent the differences in the conductivities of the ions that
are not shared between the two salts. The fact that these differences are identical for two
pairs of salts such as KCl/LiCl and KNO3 /LiNO3 tells us that the mobilities of the non-
common ions K+ and Li+ are not affected by the accompanying anions.
3.5.2. Kohlrausch's law greatly simplifies estimates of 0
 This principle is known as Kohlrausch's law of independent migration, which states
that in the limit of infinite dilution, each ionic species makes a contribution to the
conductivity of the solution that depends only on the nature of that particular ion, and is
independent of the other ions present.
Kohlrausch's law can be expressed as     
0 0 0

This means that we can assign a limiting equivalent conductivity λ0 to each kind of ion:
catio H3O+ NH4+ K+ Ba2+ Ag+ Ca2+ Sr2+ Mg2+ Na+ Li+
n
0 349.98 73.57 73.49 63.61 61.87 59.47 59.43 53.93 50.89 38.66
anion OH SO42 Br I Cl NO3 ClO3 CH3COO C2H5COO C3H7COO
  

0 197.60 80.71 78.41 76.86 76.30 71.80 67.29 40.83 35.79 32.57
Limiting ionic equivalent conductivities at 25 C, Scm1eq1
We can now estimate weak electrolyte limiting conductivities
One useful application of Kohlrausch's law is to estimate the limiting equivalent
conductivities of weak electrolytes which, as we observed above, cannot be found by
extrapolation. Thus for acetic acid CH3COOH, we combine the λ0 values for H3O+ and
CH
0
3COOH
 H0   CH
0

– 3 COO
CH3COO  given in the above table:
3.5.3. How fast do ions migrate in solution?
Movement of a migrating ion through the solution is brought about by a force
exerted by the applied electric field. This force is proportional to the field strength and to
the ionic charge. Calculations of the frictional drag are based on the premise that the ions
are spherical (not always true) and the medium is continuous (never true) as opposed to
being composed of discrete molecules. Nevertheless, the results generally seem to be
realistic enough to be useful.
According to Newton's law, a constant force exerted on a particle will accelerate it, causing it
to move faster and faster unless it is restrained by an opposing force. In the case of
electrolytic conductance, the opposing force is frictional drag as the ion makes its way
through the medium. The magnitude of this force depends on the radius of the ion and its
primary hydration shell, and on the viscosity of the solution.
Eventually these two forces come into balance and the ion assumes a constant
average velocity which is reflected in the values of λ0 tabulated in the table above.
The relation between λ0 and the velocity (known as the ionic mobility μ0) is easily
derived, but we will skip the details here, and simply present the results:
Anions are conventionally assigned negative μ0 values because they move in
opposite directions to the cations; the values shown here are absolute values |μ 0|. Note
also that the units are cm/sec per volt/cm, hence the cm2 term.
Cation H3O+ NH4+ K+ Ba2+ Ag+ Ca2+ Sr2+ Mg2+ Na+ Li+
µ0 0.362 0.0762 0.0762 0.0659 0.0642 0.0616 0.0616 0.0550 0.0520 0.0388
Anion OH SO4 Br I Cl NO3 ClO3 CH3COO C2H5COO C3H7COO
 µ0 0.2050 0.0827 0.0812 0.0796 0.0791 0.0740 0.0705 0.0461 0.0424 0.0411
Absolute limiting mobilities of ions at 25 C, (cm Volt sec )100
2 1 1

As with the limiting conductivities, the trends in the mobilities can be roughly
correlated with the charge and size of the ion. (Recall that negative ions tend to be larger
than positive ions.)
3.5.4. Cations and anions carry different fractions of the current
In electrolytic conduction, ions having different charge signs move in opposite
directions. Conductivity measurements give only the sum of the positive and negative ionic
conductivities according to Kohlrausch's law, but they do not reveal how much of the
charge is carried by each kind of ion. Unless their mobilities are the same, cations and
anions do not contribute equally to the total electric current flowing through the cell.
Recall that an electric current is defined as a flow of electric charges; the current in amperes
is the number of coulombs of charge moving through the cell per second. Because ionic
solutions contain equal quantities of positive and negative charges, it follows that the
current passing through the cell consists of positive charges moving toward the cathode,
and negative charges moving toward the anode. But owing to mobility differences, cations
and anions do not usually carry identical fractions of the charge.
Transference numbers are often referred to as transport numbers; either term is acceptable in
the context of electrochemistry.
+ Transference or transport numbers
The fraction of charge carried by a given kind of ion is known as the transference
number t+, t. For a solution of a simple binary salt,
 
t  t 
   and   
By definition, t+ + t– = 1.
To help you visualize the effects of non-identical transference numbers, consider a solution
of M+X– in which t+ = 0.75 and t– = 0.25. Let the cell be divided into three [imaginary]
sections as we examine the distribution of cations and anions at three different stages of
current flow.
+ Experimental measurement
There are two experimental techniques for the determination of transport numbers.
The Hittorf method is based on measurements of ion concentration changes near the
electrodes. The moving boundary method involves measuring the speed of displacement of
the boundary between two solutions due to an electric current.
Hittorf method
In the Hittorf method, electrolysis is carried out in a cell with three compartments:
anode, central, and cathode. Measurement of the concentration changes in the anode and
cathode compartments determines the transport numbers.The exact relationship depends
on the nature of the reactions at the two electrodes.
During electrolysis, the current carried by the anions and cations, and the amount
carried by each is proportional to its speed.
If u and v represents the speed of migration of the cation and anion, then u/(u+v)
represents the fraction of current carried by the cation, and v/(u+v) represents the fraction
of current carried by the anion, and is called its transport number or Hittorf’s number.
Hence,
current carried by the cation u
t  
Transport number of cation total current uv
current carried by the anion v
t  
Similarly, the transport number of anion total current u v
The fraction of the total current carried by the ions is directly proportional to their
velocities (Hittorf’s rule) t  t  1
Relative speed of ions during electrolysis
Consider an electrolytic vessel containing 2 Pt electrodes A and B. The vessel is
divided into three compartments AC, CD and DB, termed as anodic, central and cathodic
compartments respectively.

- Before electrolysis, the position of the solution is represented as 1 st in the diagram.

- Now, suppose that on applying potential, only two of the cation move towards the
cathode. This condition will be as represented in the diagram in 2 nd. There will be two
unpaired cations in the cathodic compartment. There will also be two unpaired anions left
in the anodic compartment. As unpaired ions always get discharged at the respective
electrodes (by the gain or loss of electrons as the case may be), two cations will be
discharged at the catode and two anions will be discharged at the anode.
- Suppose that if two cations move towards the cathode and two anions will move
towards the anode in the same time as represented by 3rd. Now four cations and four
anions will be discharged at the respective electrodes.
- Finally, if cations and anions move with different velocities so that two cations
move towards the cathode, and three anions move towards the anode. In this case, five
unpaired cations and five unpaired anions (i.e the same number) will be charged at the
respective electrodes as shown at 4th in the diagram.
- Thus, even if only cations are moving, the same number of cations and anions will
be discharged, at the respective electrodes.
- It is based on the fact that during electrolysis “the loss in amount of electrolyte
around any electrode is proportional to the speed of the ion moving away from it.
loss around cathode speed of anion v
 
loss around anode speed of cation u
Adding 1 to both sides we get
loss around anode loss around cathode u  v
 
loss around anode loss around anode u
Taking 1 to both sides, we get
loss around anode u
  t
total loss u v

- Hittorf’s apparatus consists of a two limbed vessel, connected by a narrow U-tube

in the middle. Both limbs as well as the U-tube are provided with stop-cocks at the bottom
for the withdrawal of the solution.
- The two limbs are provided with Pt electrodes. To determine the transport number
+
of Ag in AgNO3, the electrodes are either of Pt or pure Ag.
- The apparatus is filled with a standard solution of AgNO3 (usually 0.1 N) and the
cell is connected in series with a source of direct current (like battery).
 - After the electrolysis, the solutions from anodic, cathodic as well as central
compartments are withdrawn separately by opening stop-cocks at the bottom and analysed
by titration with standard ammonium thiocyanate (NH4SCN) solution.
- The change in amount of electrolyte in the these compartments is thus obtained.
Moving Boundary Method
The moving boundary method is based on the direct observation of migration of ions
under the influence of applied potential. This method is very accurate and has been used in
recent years for precision measurements. The apparatus used consists of a long vertical
tube fitted with two electrodes at the two ends (Fig. 25.7). The tube is filled with a solution
of cadmium chloride (CdCl2) at the lower end and hydrochloric acid at the upper end in a
way that there is a sharp boundary between the two (due to difference in their refractive
indices). The platinum cathode dipped in HCl solution is inserted at the top and the anode
(cadmium stick) is introduced at the bottom. On passing electric current through the
apparatus, hydrogen gas is evolved at the cathode and H+ ions move toward the anode.
The H+ ions are replaced by Cd2+ ions and hence the boundary line moves in the upward
direction. By noting the length through which the boundary moves and the quantity of
electricity passed through the cell, the transport number of H+ ion can be calculated.
 In general, if the transport number of a cation A+ is to be determined, the electrolyte
AX solution is taken in the upper part of the apparatus and a layer of another electrolyte
BX having the common ion X– is introduced in the lower part of the apparatus. The
electrolyte BX is selected so that the velocity of B+ ion is less than that of A+ ion. In such a
case, the situation is described in Fig. 25.8.

Calculations: Let c be the original concentration of A+ ions in gram-equivalents per ml of

the solution. If the distance through which boundary moves = l cm, and the area of cross-
section of the tube = A sq cm. Then the number of equivalents of A+ moving upward = A × l
× c.
Let the number of Faradays of current passed = nF
The fraction of current carried by A+ ions = nF × t+
Alc
t 
Hence,
A l  c  n  t
F  And nF
where nF = Q/F. Q being the quantity of current passed and F stands for Faraday (= 96, 500
coulombs). The above expression can now be written as
 AlcF
t 
Q
Some applications of electrolytic conduction
+ Determination of equilibrium constants by electrolytic conductance
Owing to their high sensitivity, conductance measurements are well adapted to the
measurement of equilibrium constants for processes that involve very small ion
concentrations. These include
Ks values for sparingly soluble solids
Autoprotolysis constants for solvents (such as Kw )
Acid dissociation constants for weak acids
The Degree of Dissociation
As long as the ion concentrations are so low, their values can be taken as activities, and
limiting equivalent conductivities Λ can be used directly.
 The ion product of water can be measured by conductance
Example 1: Use the appropriate limiting molar ionic conductivities to estimate the
autoprotolysis constant Kw of water at 25° C. Use the reaction equation 2 H2O → H3O+ +
OH–.
 Solubility products can be estimated from limiting ionic conductivities
Example 2: A saturated solution of silver chloride AgCl has a conductance 2.28 x 10 –6 S cm–1
at 25°C. The conductance of the water used to make up this solution is 0.116 x 10 –6 S cm–1.
The limiting ionic conductivities of the two ions are λ Ag+ = 61.9 and λCl– = 76.3 S cm2 mol–1.
Use this information to estimate the molar solubility of AgCl.
 Conductometric titration
A chemical reaction in which there is a significant change in the number or mobilities
of ionic species can be followed by monitoring the change in conductance. Many acid-base
reactions fall into this category. In conductometric titration, conductometry is employed to
detect the end-point of a titration.
Consider, for example, the titration of the strong acid HCl by the strong base NaOH. In
ionic terms, the process can be represented as H+ + Cl + Na+ + OH → H2O + Na+ + Cl
At the end point, only two ionic species remain, compared to the four during the initial
stages of the titration, so the conductivity will be at a minimum. Beyond the end point,
continued addition of base causes the conductivity to rise again. The very large mobilities
of the H+and OH– ions cause the conductivity to rise very sharply on either side of the end
point, making it quite easy to locate.
The plot on the left depicts the conductivities due to the individual ionic species. But of
course the conductivity we measure is just the sum of all of these (Kohlrausch's law of
independent migration), so the plot on the right corresponds to what you actually see when
the titration is carried out.
The factor (Va + Vb)/Vb compensates for the dilution of the solution as more base is added.
For most ordinary acid-base titrations, conductometry rarely offers any special advantage
over regular volumetric analysis or potentiometry. But in some special cases such as those
illustrated here, it is the only method capable of yielding useful results.