CHE341 Electrochemistry

Outline
• Behavior of ions in solution – electrolyte solutions, Debye-Huckel Limiting Law,
applications of DHLL
• Electrolytic conduction – molar conductivity, independent migration of ions,
Ostwald dilution law, solubility product from conductance, transport numbers
• Electrochemical cells and emf – electrolysis, Galvanic cell, thermodynamic
functions from cell emf, Nernst equation

Aims and Learning Objectives

Students will be introduced to the applications of chemical thermodynamics to
solutions and electrochemical processes.

Intended Learning Outcomes

After successfully completing this course, students should be able to:
• describe the concepts of chemical potential, ideal and non-ideal conditions, and
activity coefficients.
• use conductance measurements in investigating the behavior of electrolytes in
solution
• derive thermodynamic parameters from emf measurements
• describe electrolyte solutions in the context of the Debye-Hückel limiting law.
• calculate cell voltage using standard reduction potentials
• predict which substance will be oxidized or reduced in an aqueous electrolytic
cell.
• determine the cell potential, equilibrium constant, and free energy change for a
standard or non-standard galvanic cell.
• calculate amount of material deposited in electrolysis

Lecture notes adapted from:

1. Chemistry 2e by OpenStax. Access for free at [Link]
2e/pages/1-introduction
2. An Introduction to Aqueous Electrolyte Solutions by Margaret Robson Wright (John
Wiley & Sons) 2007.
3. Chem1 Virtual Textbook by Stephen Lower.
[Link]

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 1. Behaviour of Ions in Solution

1.1. Introduction
Electrochemistry is the study of the interchange of electrical and chemical energy.
Electrochemistry deals with chemical reactions that produce electricity and the changes
associated with the passage of electrical current through matter. The reactions involve
electron transfer, and so they are oxidation-reduction (or redox) reactions. Many metals
may be purified or electroplated using electrochemical methods. Devices such as
automobiles, smartphones, electronic tablets, watches, pacemakers, and many others use
batteries for power. Batteries use chemical reactions that produce electricity
spontaneously and that can be converted into useful work. All electrochemical systems
involve the transfer of electrons in a reacting system. In many systems, the reactions
occur in a region known as the cell, where the transfer of electrons occurs at electrodes.

Electrolytic processes – reactions in which chemical changes occur on the

passage of an electrical current
Galvanic or Voltaic processes – chemical reactions that result in the production
of electrical energy

Figure 1.1 Electric vehicles are powered by batteries, devices that harness the energy of spontaneous
redox reactions. (credit: modification of work by Robert Couse-Baker). Access for free
at [Link]

1.2. The Formation of Solutions

The formation of a solution is an example of a spontaneous process, a process that occurs
under specified conditions without the requirement of energy from some external source.
Sometimes a mixture is stirred to speed up the dissolution process, but this is not

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necessary; a homogeneous solution will form eventually. The topic of spontaneity is
critically important to the study of chemical thermodynamics and is treated more
thoroughly in a later chapter of this text. For purposes of this chapter’s discussion, it will
suffice to consider two criteria that favour, but do not guarantee, the spontaneous
formation of a solution:
1. a decrease in the internal energy of the system (an exothermic change)
2. an increased dispersal of matter in the system (which indicates an increase in
the entropy of the system)
In the process of dissolution, an internal energy change often, but not always, occurs as
heat is absorbed or evolved. An increase in matter dispersal always results when a
solution forms from the uniform distribution of solute molecules throughout a solvent.
When the strengths of the intermolecular forces of attraction between solute and solvent
species in a solution are no different than those present in the separated components,
the solution is formed with no accompanying energy change. Such a solution is called
an ideal solution. A mixture of ideal gases (or gases such as helium and argon, which
closely approach ideal behaviour) is an example of an ideal solution, since the entities
comprising these gases experience no significant intermolecular attractions.

Figure 1.2 Samples of helium and argon spontaneously mix to give a solution. Access for free
at [Link]

When containers of helium and argon are connected, the gases spontaneously mix due
to diffusion and form a solution (Figure 1.2). The formation of this solution clearly involves
an increase in matter dispersal, since the helium and argon atoms occupy a volume twice
as large as that which each occupied before mixing.

Ideal solutions may also form when structurally similar liquids are mixed. For example,
mixtures of the alcohols methanol (CH3OH) and ethanol (C2H5OH) form ideal solutions, as
do mixtures of the hydrocarbons pentane, C5H12, and hexane, C6H14. Placing methanol
and ethanol, or pentane and hexane, in the bulbs shown in Figure 2 will result in the
same diffusion and subsequent mixing of these liquids as is observed for the He and Ar
gases (although at a much slower rate), yielding solutions with no significant change in
energy. Unlike a mixture of gases, however, the components of these liquid-liquid
solutions do, indeed, experience intermolecular attractive forces. But since the molecules
of the two substances being mixed are structurally very similar, the intermolecular

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attractive forces between like and unlike molecules are essentially the same, and the
dissolution process, therefore, does not entail any appreciable increase or decrease in
energy. These examples illustrate how increased matter dispersal alone can provide the
driving force required to cause the spontaneous formation of a solution. In some cases,
however, the relative magnitudes of intermolecular forces of attraction between solute
and solvent species may prevent dissolution.

Three types of intermolecular attractive forces are relevant to the dissolution process:
solute-solute, solvent-solvent, and solute-solvent. As illustrated in Figure 1.3, the
formation of a solution may be viewed as a stepwise process in which energy is consumed
to overcome solute-solute and solvent-solvent attractions (endothermic processes) and
released when solute-solvent attractions are established (an exothermic process referred
to as solvation). The relative magnitudes of the energy changes associated with these
stepwise processes determine whether the dissolution process overall will release or
absorb energy. In some cases, solutions do not form because the energy required to
separate solute and solvent species is so much greater than the energy released by
solvation.

Figure 1.3 This schematic representation of dissolution shows a stepwise process involving the
endothermic separation of solute and solvent species (Steps 1 and 2) and exothermic solvation (Step 3).
Access for free at [Link]

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 1.3. Electrolyte Solutions
When some substances are dissolved in water, they undergo either a physical or a
chemical change that yields ions in solution. These substances constitute an important
class of compounds called electrolytes. Substances that do not yield ions when dissolved
are called nonelectrolytes. If the physical or chemical process that generates the ions is
essentially 100% efficient (all of the dissolved compound yields ions), then the substance
is known as a strong electrolyte. If only a relatively small fraction of the dissolved
substance undergoes the ion-producing process, it is called a weak electrolyte.

Substances may be identified as strong, weak, or nonelectrolytes by measuring the

electrical conductance of an aqueous solution containing the substance. To conduct
electricity, a substance must contain freely mobile, charged species. Most familiar is the
conduction of electricity through metallic wires, in which case the mobile, charged entities
are electrons. Solutions may also conduct electricity if they contain dissolved ions, with
conductivity increasing as ion concentration increases. Applying a voltage to electrodes
immersed in a solution permits assessment of the relative concentration of dissolved ions,
either quantitatively, by measuring the electrical current flow, or qualitatively, by
observing the brightness of a light bulb included in the circuit.

Figure 1.4 Solutions of nonelectrolytes such as ethanol do not contain dissolved ions and cannot conduct
electricity. Solutions of electrolytes contain ions that permit the passage of electricity. The conductivity of
an electrolyte solution is related to the strength of the electrolyte. Access for free
at [Link]

Ionic Electrolytes
Water and other polar molecules are attracted to ions, as shown in Figure 1.5. The
electrostatic attraction between an ion and a molecule with a dipole is called an ion-
dipole attraction. These attractions play an important role in the dissolution of ionic
compounds in water.

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When ionic compounds dissolve in water, the ions in the solid separate and disperse
uniformly throughout the solution because water molecules surround and solvate the
ions, reducing the strong electrostatic forces between them. This process represents a
physical change known as dissociation. Under most conditions, ionic compounds will
dissociate nearly completely when dissolved, and so they are classified as
strong electrolytes. Even sparingly, soluble ionic compounds are strong electrolytes,
since the small amount that does dissolve will dissociate completely.

Figure 1.5 As potassium chloride (KCl) dissolves in water, the ions are hydrated. The polar water molecules
are attracted by the charges on the K + and Cl− ions. Water molecules in front of and behind the ions are
not shown. Access for free at [Link]

Consider what happens at the microscopic level when solid KCl is added to water. Ion-
dipole forces attract the positive (hydrogen) end of the polar water molecules to the
negative chloride ions at the surface of the solid, and they attract the negative (oxygen)
ends to the positive potassium ions. The water molecules surround individual K+ and
Cl− ions, reducing the strong interionic forces that bind the ions together and letting
them move off into solution as solvated ions, as Figure 3 shows. Overcoming the
electrostatic attraction permits the independent motion of each hydrated ion in a dilute
solution as the ions transition from fixed positions in the undissolved compound to widely
dispersed, solvated ions in solution.

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Covalent Electrolytes
Pure water is an extremely poor conductor of electricity because it is only very slightly
ionized—only about two out of every 1 billion molecules ionize at 25 °C. Water ionizes
when one molecule of water gives up a proton (H+ ion) to another molecule of water,
yielding hydronium and hydroxide ions.
H2O(l) + H2O(l) ⇌ H3O+(aq) + OH−(aq)
In some cases, solutions prepared from covalent compounds conduct electricity because
the solute molecules react chemically with the solvent to produce ions. For example, pure
hydrogen chloride is a gas consisting of covalent HCl molecules. This gas contains no
ions. However, an aqueous solution of HCl is a very good conductor, indicating that an
appreciable concentration of ions exists within the solution.
Because HCl is an acid, its molecules react with water, transferring H+ ions to form
hydronium ions (H3O+) and chloride ions (Cl−):

This reaction is essentially 100% complete for HCl (i.e., it is a strong acid and,
consequently, a strong electrolyte). Likewise, weak acids and bases that only react
partially generate relatively low concentrations of ions when dissolved in water and are
classified as weak electrolytes. The reader may wish to review the discussion of strong
and weak acids provided in the earlier chapter of this text on reaction classes and
stoichiometry.

1.4. Ideal and Non-Ideal Electrolyte Solutions

Electrolyte solutions are mixtures where the components are the solute and the solvent.
When the concentration of the solute tends to zero, called infinite dilution, the solution
is regarded as ideal. When there are finite concentrations of the solute the solution is
regarded as non-ideal.

In electrolyte solutions there will be interactions between solute – solute particles, solute
– solvent particles and solvent – solvent particles.

In the ideal electrolyte solutions all three interactions are present:

• ion – ion interactions

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 • ion – solvent interactions
• solvent – solvent interactions
But the concentration of ions tends to zero. Therefore, solvent – solvent interactions are
the most significant.

Non-idealilty corresponds to all ion-ion, ion-solvent, and solvent-solvent interactions

which are over and above those considered to be present in the ideal solution resulting
from an increase in solute concentration.

1.5. Macroscopic Manifestation of Non-Ideality

For an ideal (id) solution, the chemical potential of each component is

𝜇𝑖𝑖𝑑 = 𝜇𝑖° + 𝑅𝑇 ln 𝑥𝑖 (1.5.1)

Therefore

𝜇𝑖𝑖𝑑 − 𝜇𝑖°
𝑥𝑖 = exp [ ] (1.5.2)
𝑅𝑇

For easy comparison, we define the activity 𝑎𝑖 of a substance in any solution as

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 𝜇𝑖 − 𝜇𝑖°
𝑎𝑖 = exp [ ] (1.5.3)
𝑅𝑇

And so for any solution

𝜇𝑖 = 𝜇𝑖° + 𝑅𝑇 ln 𝑎𝑖 (1.5.4)

𝑎𝑖 = 𝑥𝑖 in an ideal solution

The difference between real solution chemical potential and an ideal solution chemical
potential is
𝑎𝑖
𝜇𝑖 − 𝜇𝑖𝑖𝑑 = 𝑅𝑇 ln 𝑎𝑖 − 𝑅𝑇 ln 𝑥𝑖 = 𝑅𝑇 ln ( ) (1.5.5)
𝑥𝑖

𝑎𝑖
The ratio is thus a measure of the departure from ideal behaviour.
𝑥𝑖

We therefore define the activity coefficient 𝛾𝑖 of component i as

𝑎𝑖
𝛾𝑖 = (1.5.6)
𝑥𝑖

So that
𝑎𝑖 = 𝛾𝑖 𝑥𝑖 (1.5.7)

Thus, the activity coefficient 𝛾𝑖 measures the degree of departure of substance i from ideal
behaviour.

1.6. Activity Coefficient,  in Terms of Molality

The molality of a solute i is
𝑛𝑖
𝑚𝑖 = (1.6.1)
𝑛𝐴 𝑀𝐴

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where 𝑀𝐴 is molar mass of solvent and 𝑛𝐴 is moles of solvent.

Thus

𝑚𝑖 𝑛𝑖 𝑥𝑖 𝑛𝑡𝑜𝑡
= 𝑎𝑛𝑑 𝑚𝑖 = (1.6.2)
𝑛𝑡𝑜𝑡 𝑛𝑡𝑜𝑡 𝑛𝐴 𝑀𝐴 𝑛𝐴 𝑀𝐴

and
𝑥𝑖 = 𝑚𝑖 𝑥𝐴 𝑀𝐴 (1.6.3)

The 𝜇𝑖 expression becomes

𝑚°
𝜇𝑖 = 𝜇𝑖° + 𝑅𝑇 ln (𝛾𝑖 𝑚𝑖 𝑥𝐴 𝑀𝐴 ) (1.6.4)
𝑚°

Or
𝑚𝑖
𝜇𝑖 = 𝜇𝑖° + 𝑅𝑇 ln(𝑀𝐴 𝑚° ) + 𝑅𝑇 ln (𝛾𝑖 𝑥𝐴 ) (1.6.5)
𝑚°

mol
𝑚° ≡ 1 used to keep equations dimensionally correct
kg
18g 1mol
E.g. for H2 O 𝑀𝐴 𝑚° = mol × = 0.018
kg

Thus
°
𝑚𝑖
𝜇𝑖 = 𝜇𝑚,𝑖 + 𝑅𝑇 ln (𝛾𝑚,𝑖 ) (1.6.6)
𝑚°

°
We call 𝛾𝑚,𝑖 the molality-scale activity coefficient of solute i and 𝜇𝑚,𝑖 the molality-scale
standard state chemical potential of i.

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 1.6.1. Mean Activity Coefficients
Consider a solution composed of a non-electrolyte solvent and a single electrolyte that
yield only two kinds of ions:

𝑀𝑣+ 𝑋𝑣− → 𝑣+ 𝑀+ + 𝑣− 𝑋 − (1.6.7)

If the chemical potential of a univalent cation 𝑀 + is denoted 𝜇+ and that of a univalent

anion 𝑋 − is denoted 𝜇− , then

𝜇𝑖 = 𝑣+ 𝜇+ + 𝑣− 𝜇− (1.6.8)

Then
𝑚+ 𝑚−
𝜇𝑖 = 𝑣+ 𝜇+° + 𝑣− 𝜇−° + 𝑣+ 𝑅𝑇 ln (𝛾+ °
) + 𝑣− 𝑅𝑇 ln (𝛾− ° ) (1.6.9)
𝑚 𝑚

𝑦 ln(𝑎𝑏) = ln(𝑎𝑏)𝑦 = ln 𝑎 𝑦 + ln 𝑏 𝑦

𝑚+ 𝑣+ 𝑚− 𝑣−
𝜇𝑖 = 𝑣+ 𝜇+° + 𝑣− 𝜇−° + 𝑅𝑇 ln [(𝛾+ )𝑣+ (𝛾− )𝑣− ( ) ( °) ] (1.6.10)
𝑚° 𝑚
Because 𝜇+ and 𝜇− cannot be determined experimentally, the single ion activity
coefficients 𝛾+ and 𝛾− cannot be measured. The combination (𝛾+ )𝑣+ (𝛾− )𝑣− that occurs in
the experimentally measurable quantity 𝜇𝑖 in Equation 16 is measurable.

We therefore define the molality-scale mean activity coefficient 𝛾± of the electrolyte

𝑀𝑣+ 𝑋𝑣− as:

(𝛾± )𝑣++𝑣− ≡ (𝛾+ )𝑣+ (𝛾− )𝑣− (1.6.11)

Example 1: Mean Activity Coefficient

For Ba(NO3)2

𝑣+ = 1 and 𝑣− = 2
Therefore

(𝛾± )𝑣++𝑣− = (𝛾± )3 = (𝛾+ )1 (𝛾− )2

and
1⁄ 2
𝛾± = (𝛾+ ) 3 (𝛾− ) ⁄3

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 1.7. Debye-Hückel Limiting Law
The Debye-Hückel theory gives theoretical expressions for calculating the activity
coefficient of any species in solution.

log 𝛾± = −𝐴|𝑧+ 𝑧− |√𝐼 (1.7.1)

where 𝑧+ and 𝑧− are the ionic charges.

A = 0.509 mol−1/2 dm 3/2 for water at 25 C

I is the ionic strength given by:

1
𝐼 = ∑ 𝑐𝑖 𝑧𝑖 2 (1.7.2)
2
𝑖

where c is the concentration.

Example 2: Calculating Ionic Strength of a Solution

For 1 M NaCl(aq)

𝑐+ = 1 𝑀; 𝑐− = 1 𝑀; 𝑧+ = 1; 𝑧− = −1

Therefore

1
𝐼 = ∑ 𝑐𝑖 𝑧𝑖 2
2
𝑖

1
𝐼 = {1𝑀(+1)2 + 1𝑀(−1)2 } = 1𝑀
2

Example 3: Activity Coefficient from the Debye-Hückel Limiting Law

For a 0.001 M CaCl2(aq) solution at 298 K, calculate:
(a) the ionic strength
(b) the activity coefficients of the Ca2+ and Cl− ions
(c) the mean activity coefficient
(d) Check the answers to (b) and (c) for consistency.

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Solution
(a) The ionic strength is
1
𝐼 = ∑ 𝑐𝑖 𝑧𝑖 2
2
𝑖

1
𝐼 = [0.001𝑀(+2)2 + 0.002𝑀(−1)2 ] = 0.003 𝑀
2

(b) Activity coefficients

log 𝛾+ = −0.509(𝑧+ )2√𝐼
1 1
𝑚𝑜𝑙 −2 𝑚𝑜𝑙 2
log 𝛾𝐶𝑎2+ = −0.509 ( 3 ) (2)2 (0.003 )
𝑑𝑚 𝑑𝑚3

𝛾𝐶𝑎2+ = 0.774

𝛾𝐶𝑙− = 0.938

(c) Mean activity coefficient

log 𝛾± = −0.509|𝑧+ 𝑧− |√𝐼
1 1
𝑚𝑜𝑙 −2 𝑚𝑜𝑙 2
log 𝛾± = −0.509 ( 3 ) |2 × (−1)| (0.003 )
𝑑𝑚 𝑑𝑚3

𝛾± = 0.880

(d) For CaCl2

𝑣+ = 1 and 𝑣− = 2

(𝛾± )𝑣++𝑣− = (𝛾± )3 = (𝛾𝐶𝑎2+ )1 (𝛾𝐶𝑙− )2

And
1⁄ 2
𝛾± = (𝛾𝐶𝑎2+ ) 3 (𝛾𝐶𝑙− ) ⁄3

1⁄ 2
𝛾± = (0.774) 3 (0.938) ⁄3

𝛾± = 0.880

The Debye-Huckel limiting law: log 𝛾± = −𝐴|𝑧+ 𝑧− |√𝐼 is valid in very dilute solutions
corresponding to ionic strengths less than 0.001 M. For moderate concentration
solutions corresponding to ionic strengths in the range 0.001 M to 0.1 M the Debye-
Huckel equation

√𝐼
log 𝛾± = −𝐴|𝑧+ 𝑧− | (1.7.3)
1 + √𝐼
is used.

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Example 4: Activity Coefficient from the Debye-Hückel Limiting Law
(a) Calculate the ionic strength, I, for 0.05 M solutions of KCl(aq), MgSO4(aq) and
LaFe(CN)6(aq).
√𝐼
(b) Using the equation, log 𝛾𝑖 = −𝐴𝑧𝑖 2 1+√𝐼 calculate the activity coefficients for K+(aq),
Mg2+(aq) and La3+(aq) ions for solutions of ionic strengths equal to 0.1 M.
Comment on these values and give a brief explanation for the difference in the
values.
(c) Now calculate the activity coefficients for K+(aq), Mg2+(aq) and La3+(aq) ions in the
original solutions of concentration equal to 0.05 M, and compare the results with
those from part (b).

Solution
(a) The ionic strength is
1
𝐼 = ∑ 𝑐𝑖 𝑧𝑖 2
2
𝑖

For KCl(aq)

1
𝐼 = [0.05𝑀 × 12 + 0.05𝑀 × 12 ] = 0.05 𝑀
2

For MgSO4(aq)

1
𝐼 = [0.05𝑀 × 22 + 0.05𝑀 × 22 ] = 0.20 𝑀
2

For LaFe(CN)6(aq)
1
𝐼 = [0.05𝑀 × 32 + 0.05𝑀 × 32 ] = 0.45 𝑀
2

The calculation show the dramatic increase in the ionic strength which occurs as the
charge on the ions increases, despite all the solutions being of the same concentration.
Non-ideality will be expected to increase in line with increasing ionic strength.

(b) Activity coefficient

√𝐼
log 𝛾𝑖 = −𝐴𝑧𝑖 2
1 + √𝐼
1 1
𝑚𝑜𝑙 −2 √0.10 𝑚𝑜𝑙 2
log 𝛾𝐾+ = −0.509 ( 3 ) × 12 × ( 3)
𝑑𝑚 1 + √0.10 𝑑𝑚

log 𝛾𝐾+ = −0.509 × 1 × 0.240 = −0.1223

∴ 𝛾𝐾+ = 0.7545
1 1
𝑚𝑜𝑙 −2 √0.10 𝑚𝑜𝑙 2
log 𝛾𝑀𝑔2+ = −0.509 ( 3 ) × 22 × ( 3)
𝑑𝑚 1 + √0.10 𝑑𝑚

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 log 𝛾𝑀𝑔2+ = −0.509 × 4 × 0.240 = −0.490

∴ 𝛾𝑀𝑔2+ = 0.324

1 1
𝑚𝑜𝑙 −2 √0.10 𝑚𝑜𝑙 2
log 𝛾𝐿𝑎3+ = −0.509 ( 3 ) × 32 × ( 3)
𝑑𝑚 1 + √0.10 𝑑𝑚

log 𝛾𝐿𝑎3+ = −0.509 × 9 × 0.240 = −1.102

∴ 𝛾𝐿𝑎3+ = 0.0793

These are activity coefficients calculated for the same ionic strength. The decreasing
values
𝛾𝐾+ > 𝛾𝑀𝑔2+ > 𝛾𝐿𝑎3+

reflect the increasing non-ideality as a result of increasing ionic interactions which are a
consequence of increasing charge on the ion.

(c) Activity coefficient

√𝐼
log 𝛾𝑖 = −𝐴𝑧𝑖 2
1 + √𝐼

0.05 M KCl has an ionic charge of 0.05 M

1 1
𝑚𝑜𝑙 −2 √0.05 𝑚𝑜𝑙 2
log 𝛾𝐾+ = −0.509 ( 3 ) × 12 × ( 3)
𝑑𝑚 1 + √0.05 𝑑𝑚

log 𝛾𝐾+ = −0.509 × 1 × 0.1827 = −0.093

∴ 𝛾𝐾+ = 0.807

0.05 M MgSO4 has an ionic charge of 0.20 M

1 1
𝑚𝑜𝑙 −2 √0.20 𝑚𝑜𝑙 2
log 𝛾𝑀𝑔2+ = −0.509 ( 3 ) × 22 × ( 3)
𝑑𝑚 1 + √0.20 𝑑𝑚

log 𝛾𝑀𝑔2+ = −0.509 × 4 × 0.309 = −0.630

∴ 𝛾𝑀𝑔2+ = 0.234

0.05 M LaFe(CN)6 has an ionic charge of 0.45 M

1 1
𝑚𝑜𝑙 −2 √0.45 𝑚𝑜𝑙 2
log 𝛾𝐿𝑎3+ = −0.509 ( 3 ) × 32 × ( 3)
𝑑𝑚 1 + √0.45 𝑑𝑚

log 𝛾𝐿𝑎3+ = −0.509 × 9 × 0.401 = −1.843

∴ 𝛾𝐿𝑎3+ = 0.014

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Compiled by Dr Tlhabologo M Kabomo, Department of Chemistry, University of Botswana
Gathering all the calculations together gives the following table:

The results show that increasing both the ionic strength and charge results in a dramatic
decrease in the activity coefficient, with the decrease being greatest for the most highly
charged ion. This reflects the increasing non-ideality as both charge and the ionic
strength increase.

1.8. Some Applications of Debye-Hückel Limiting Law

1.8.1. Equilibrium Constant

Consider the dissociation of a weak 1:1 electrolyte

𝐴𝐵 ⇌ 𝐴+ + 𝐵 − (1.8.1)

The thermodynamic equilibrium constant is given by

(𝑎𝐴+ )(𝑎𝐵− )
𝐾𝑇 = (1.8.2)
𝑎𝐴𝐵

(𝑐𝐴+ 𝛾+ )(𝑐𝐵− 𝛾− )
𝐾𝑇 = (1.8.3)
𝑐𝐴𝐵 𝛾𝐴𝐵

𝑐𝐴+ 𝑐𝐵− 𝛾±2

𝐾𝑇 = × (1.8.4)
𝑐𝐴𝐵 𝛾𝐴𝐵

𝐹𝑜𝑟 1: 1 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑙𝑦𝑡𝑒 𝛾±2 = 𝛾+ 𝛾−

At low concentration for a weak electrolyte 𝛾𝐴𝐵 ≈ 1. So,

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Compiled by Dr Tlhabologo M Kabomo, Department of Chemistry, University of Botswana
 𝛾±2 𝑐𝐴+ 𝑐𝐵−
𝐾𝑇 = 𝐾𝑐 × = 𝐾𝑐 𝛾±2 𝐾𝑐 = (1.8.5)
𝛾𝐴𝐵 𝑐𝐴𝐵

Taking logs

log 𝐾𝑇 = log 𝐾𝑐 + 2 log 𝛾± (1.8.6)

Applying DHLL log 𝛾± = −𝐴|𝑧+ 𝑧− |√𝐼

log 𝐾𝑇 = log 𝐾𝑐 − 2𝐴|𝑧+ 𝑧− |√𝐼 (1.8.7)

Or

log 𝐾𝑐 = log 𝐾𝑇 + 2𝐴|𝑧+ 𝑧− |√𝐼 (1.8.8)

So the determination of Kc at different ionic strengths results in a linear plot.

1.8.2. Solubility and Ionic Strength for a Sparingly Soluble Salt

The Solubility Product
When a slightly soluble ionic compound is added to water, some of it dissolves to form
a solution, establishing an equilibrium between the pure solid and a solution of its ions.
For the dissolution of calcium phosphate, one of the two main components of kidney
stones, the equilibrium can be written as follows, with the solid salt on the left:

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Compiled by Dr Tlhabologo M Kabomo, Department of Chemistry, University of Botswana
 Ca3 (PO4 )2 (𝑠) ⇌ 3Ca2+ (𝑎𝑞) + 2PO3−
4 (𝑎𝑞) (1.8.9)

The equilibrium constant for the dissolution of a sparingly soluble salt is the solubility
product (Ksp) of the salt. Because the concentration of a pure solid such as Ca3(PO4)2 is a
constant, it does not appear explicitly in the equilibrium constant expression. The
equilibrium constant expression for the dissolution of calcium phosphate is therefore

[Ca2+ ]3 [PO3−
4 ]
2
𝐾= (1.8.10)
[Ca3 (PO4 )3 ]

𝐾[Ca3 (PO4 )3 ] = 𝐾𝑠𝑝 = [Ca2+ ]3 [PO3−

4 ]
2 (1.8.11)

At 25°C and pH 7.00, Ksp for calcium phosphate is 2.07 × 10−33, indicating that the
concentrations of Ca2+ and PO43− ions in solution that are in equilibrium with solid calcium
phosphate are very low.

For a sparingly soluble 1:1 salt, correcting for non-ideality

𝐾𝑠𝑝 = 𝑎+ 𝑎− = 𝑐+ 𝑐− 𝛾±2 (1.8.12)

For a solution in which ions of a sparingly soluble 1:1 salt originate only from the salt
substance itself but in which there may be significant concentration of other ions, the
solubility of the sparingly soluble salt is by

𝑆 ≈ 𝑐+ = 𝑐− (1.8.13)
and
𝐾𝑠𝑝 = 𝑆 2 𝛾±2 (1.8.14)

Example 5 : Solubility and Ionic Strength for a Sparingly Soluble Salt

Hg2Cl2 is sparingly soluble in water at 25 C, solubility is 6.5  10−7 mol dm−3.
(a) Calculate the solubility product and explain why it is not necessary to correct for
non-ideality.
(b) Calculate the solubility in 0.100 mol dm−3 KNO3 solution.
(c) Compare the solubility in the two solutions.

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Compiled by Dr Tlhabologo M Kabomo, Department of Chemistry, University of Botswana
Solution
(a) Hg 2 Cl2 (𝑠) ⇌ Hg 2+ −
2 (𝑎𝑞) + 2Cl (𝑎𝑞)

𝐾𝑠𝑝 = ([Hg 2+ − 2
2 ][Cl ] )𝑒𝑞

If the solubility in water is S, then [Hg 2+ −

2 ] = 𝑆 and [Cl ] = 2𝑆

𝐾𝑠𝑝 = 𝑆 × (2𝑆)2 = 4𝑆 3
𝐾𝑠𝑝 = 4 × (6.5 × 10−7 )3 𝑚𝑜𝑙 3 𝑑𝑚−9
𝐾𝑠𝑝 = 1.1 × 10−18 𝑚𝑜𝑙 3 𝑑𝑚−9

The solubility of Hg2Cl2 is so low that the saturated solution will be dilute as to be
ideal. Hence corrections for non-ideality are not needed.

(b) In 0.100 mol dm−3 KNO3(aq) correction for non-ideality will have to be made.

1
𝐼 = ∑ 𝑐𝑖 𝑧𝑖 2 = 0.100 𝑚𝑜𝑙 𝑑𝑚−3
2
𝑖

∴ √𝐼 = 0.3162 𝑚𝑜𝑙1/2 𝑑𝑚−3/2

2
𝐾𝑠𝑝 = 𝑎𝐻𝑔22+ 𝑎𝐶𝑙 −

𝐾𝑠𝑝 = [𝐻𝑔22+ ]𝛾𝐻𝑔22+ [𝐶𝑙 − ]2 𝛾𝐶𝑙

2
−

3 2 3 3
𝐾𝑠𝑝 = 4𝑆 ′ 𝛾𝐻𝑔22+ 𝛾𝐶𝑙 ′
− = 4𝑆 𝛾±

√𝐼
log 𝛾± = −𝐴|𝑧+ 𝑧− |
1 + √𝐼
1 1
𝑚𝑜𝑙 −2 √0.10 𝑚𝑜𝑙 2
log 𝛾± = −0.509 ( 3 ) × 2 × 1 × ( 3)
𝑑𝑚 1 + √0.10 𝑑𝑚

log 𝛾± = −0.245

∴ 𝛾± = 0.569
3
𝐾𝑠𝑝 = 4𝑆 ′ 𝛾±3

3
𝐾𝑠𝑝 = 4𝑆 ′3 × (0.569)3 = 0.736𝑆 ′ = 1.1 × 10−18 𝑚𝑜𝑙 3 𝑑𝑚−9

3
𝑆 ′ = 1.495 × 10−18 𝑚𝑜𝑙 3 𝑑𝑚−9

∴ 𝑆 ′ = 1.14 × 10−6 𝑚𝑜𝑙 𝑑𝑚−3

(c) Non-ideality causes the solubility to increase by a factor of 1.75

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 2. Electrolytic Conductance

2.1. Basics of ionic conduction

The conduction of electricity through an ionic solution is different from metallic
conduction in two fundamental ways:

• The current is associated with the transport of relatively large and massive
hydrated ions, rather than by nearly weightless electrons. Electrons move largely
unimpeded through the metal. But ions, with their closely held waters of hydration
and more diffuse secondary hydration shell and oppositely-charged counterions,
must disrupt the local hydrogen-bonded water structure as they move through
the solution.
• Transfer of electric charge into and out of the solution occurs at electrodes and is
accompanied by chemical reactions at these interfaces.

Electrolytic conduction involves the transport of electric charge in the form of hydrated
ions. Movement of these ions in response to an electric potential gradient is known as
migration.

Electric charge is measured in units of coulombs. A coulomb is an ampere-second;

if a current of 1 amp flows for one minute, the quantity of charge transported will
be 3600 C.

When charges migrate in an electric field, thermodynamic work is done. One C of

charge moving through a potential difference of one volt results in the
performance of one joule of work.

2.1.1. Electrical resistance, conductance, and conductivity

Ionic migration is always impeded by the drag created by the hydration shell as the ions
break their way through the hydrogen-bonded water structure. Electrolytic conduction is
therefore always associated with a certain amount of electrical resistance. Electrical
resistance is defined by Ohm's law:

𝑉
𝑅= (2.1.1)
𝐼

in which V is the potential difference (voltage) and i is the current. Resistance is expressed
in ohms, whose symbol is Ω (omega).

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Compiled by Dr Tlhabologo M Kabomo, Department of Chemistry, University of Botswana
Resistance is an extensive property because it depends on the thickness and cross-
section area of the material through which the current flows. The intensive analogue of
resistance is the resistivity ρ (rho), defined as the resistance between opposite faces of a
1-cm cube. Resistivity is usually expressed in ohm-cm.

𝐴 𝑙
𝜌 = 𝑅( ) (𝑅 = 𝜌 × ) (2.1.2)
𝑙 𝐴

In working with electrolytic solutions, it is more convenient to use the corresponding

reciprocal properties:

𝑙
𝜅 = 𝐺( ) (2.1.3)
𝐴
1
𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑎𝑛𝑐𝑒, 𝐺 = (2.1.4)
𝑅
1
𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑖𝑣𝑖𝑡𝑦, 𝜅 = (2.1.5)
𝜌

The SI unit of conductance is the siemens, indicated by the symbol S. Conductivity, the
reciprocal of the resistivity, is frequently expressed in ohm–1 cm–1
–1 –1
or S cm , but the SI units are S m .

[Link]. Conductance measurements

The traditional method of measuring resistance or conductance is by means of a
Wheatstone bridge arrangement in which a known resistance is balanced against the
unknown resistance. The latter consists of a conductivity cell having electrodes of fixed
size and spacing. Nowadays it is more common to employ a digital measuring device.

Figure 2.1 Wheatstone bridge circuit

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Compiled by Dr Tlhabologo M Kabomo, Department of Chemistry, University of Botswana
The solution is contained in a conductance cell placed in a thermostat bath to maintain
constant temperature, and when a current is passed the experiment measures the
resistance, or conductance, of the solutions contained between the electrodes (Figure
2.2). The length 𝑙 is the distance apart of the electrodes, and the quotient 𝑙 ⁄𝐴 is called
the cell constant, and has units length–1, generally cm–1.

Figure 2.2 Schematic diagram for an apparatus for determining conductance of a solution.

Knowing the resistance 𝑅, or conductance,𝐺, the length 𝑙 and the cross-sectional area, 𝐴,
the conductivity, 𝜅, can be found from:

𝑙 1 𝑙
𝜅 = 𝐺( ) = ( ) (2.1.6)
𝐴 𝑅 𝐴

In practical measurements of conductivity, no attempt is made to define the precise

dimensions of the conductive path. Instead, the conductance cell is first calibrated by
filling it with a standardized solution of potassium chloride, for which extensive
conductivity data is available.

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Compiled by Dr Tlhabologo M Kabomo, Department of Chemistry, University of Botswana
Example 2.1: Conductance measurement
A conductivity cell has a resistance of 747.5 Ω when it is filled with 0.0100 M solution
of KCl and a resistance of 876 Ω when it is filled with 0.005 M CaCl2 solution, both at
25 oC. Calculate the conductivity of the CaCl2 solution given the following conductivities
of KCl solutions.

Concentration, 𝜿, 𝛀 𝒎
−𝟏 −𝟏
(S 𝒎
−𝟏
)
−𝟏
𝒎𝒐𝒍 L 0 oC 18 oC 25 oC
1 6.543 9.820 11.173
0.1 0.7154 1.1192 1.2886
0.01 0.07751 0.12227 0.14114

Solution
The conductance of the cell filled with KCl solution is

𝐴 1
𝐺 = 𝜅 ( ) = = 0.001338 𝛺 −1
𝑙 𝑅
−1 −1
The conductivity of the solution from the table is 0.14114 𝛺 𝑚 . The cell constant
is
−1 −1
𝑙 𝜅 0.14114 Ω m −1
= = −1
= 105.5 𝑚
𝐴 𝐺 0.001338 Ω

The conductivity of the CaCl2 solution can now be obtained from

−1
𝑙 𝑙 1 105.5 m −1 −1
𝜅 = 𝐺( )= ( ) = = 0.1204 Ω m
𝐴 𝐴 𝑅 876 Ω

2.1.2. Molar conductivity

The conductance of a solution depends on 1) the concentration of the ions it
contains, 2) on the number of charges carried by each ion, and 3) on the mobilities of
these ions. The latter term refers to the ability of the ion to make its way through the
solution, either by ordinary thermal diffusion or in response to an electric potential
gradient.
The first step in comparing the conductance of different solutes is to reduce them to a
common concentration. For this, we define the conductance per unit concentration, which
is known as the molar conductivity, denoted by the upper-case Greek lambda:

𝜅
Λm = (2.1.7)
𝑐𝑠𝑡𝑜𝑖𝑐ℎ

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Compiled by Dr Tlhabologo M Kabomo, Department of Chemistry, University of Botswana
Example 2.2 Molar conductivity measurements
A conductance cell containing 0.01000 mol dm-3 KCl solution was found to have a
resistance of 2573 ohm at 25 oC, and a conductivity of 1.409  10-3 S cm-3. The same
cell when filled with a 0.0200 mol dm-3 solution of CH3COOH has a resistance of 5085
ohm. Calculate:
(a) The cell constant
(b) The conductivity of the CH3COOH solution
(c) The molar conductivity of the KCl and of the CH3COOH solution
(d) Comment on the results.

Solution
a) The conductivity and the resistance of KCl solution are given, from which the cell
constant can be found.

𝑙 1 𝑙
𝜅 = 𝐺( ) = ( )
𝐴 𝑅 𝐴

𝑙
∴ ( ) = 𝜅𝑅 = 1.409 × 10−3 Ω−1 cm−1 × 2573 Ω = 3.625 cm−1
𝐴

b) The conductivity of CH3COOH is

1 𝑙 3.625 cm−1
𝜅= ( )= = 7.129 × 10−4 Ω−1 cm−1
𝑅 𝐴 5085 Ω

c) The molar conductivity is

𝜅
Λm =
𝑐

7.129 × 10−4 S cm−1

Λ m, CH3COOH = = 3.56 S cm2 mol−1
0.2000 × 10−3 mol cm−3

1.409 × 10−4 S cm−1

Λ m, KCl = = 140.9 S cm2 mol−1
0.01000 × 10−3 mol cm−3

d) The molar conductivity of the acetic acid solution is much lower than that for the
KCl solution, despite a factor of 20 in the concentration. This is a direct reflection
of the fact that KCl is known to be a strong electrolyte, whereas acetic acid is a
weak electrolyte.

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Compiled by Dr Tlhabologo M Kabomo, Department of Chemistry, University of Botswana
 2.1.3. Dependence of molar conductivity on concentration
Studies have shown that conductivities of electrolytes all diminish with concentration (or
more accurately, with the square root of the concentration), but they do so in several
distinct ways that are distinguished by their behaviours at very small concentrations. This
led to the classification of electrolytes as weak, intermediate, and strong.

Figure 2.2 Variation of conductivity with concentration for various electrolytes

You will notice that plots of conductivities vs. c start at c = 0. It is of course impossible
to measure the conductance of an electrolyte at vanishingly small concentrations (not to
mention zero!), but for strong and intermediate electrolytes, one can extrapolate a series
of observations to zero. The resulting values are known as limiting molar conductance or
sometimes as "molar conductance at infinite dilution", designated by Λ°.

[Link]. Strong electrolytes

For the ideal case the conductivity  would be expected to be strictly proportional to the
concentration of ions actually present. That is

𝜅 ∝ 𝑐𝑎𝑐𝑡𝑢𝑎𝑙 (2.1.8)

The molar conductivity is defined as

𝜅
Λm = (2.1.7)
𝑐𝑠𝑡𝑜𝑖𝑐ℎ

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Compiled by Dr Tlhabologo M Kabomo, Department of Chemistry, University of Botswana
and so
𝑐𝑎𝑐𝑡𝑢𝑎𝑙
Λ= (2.1.9)
𝑐𝑠𝑡𝑜𝑖𝑐ℎ

But for a strong electrolyte:

𝑐𝑎𝑐𝑡𝑢𝑎𝑙 = 𝑐𝑠𝑡𝑜𝑖𝑐ℎ (2.1.10)

𝑐𝑠𝑡𝑜𝑖𝑐ℎ
∴Λ∝ = constant (2.1.11)
𝑐𝑠𝑡𝑜𝑖𝑐ℎ

Therefore, for a strong electrolyte under ideal conditions the molar conductance is
expected to be independent of concentration. However, when measurements are made
on strong electrolyte solutions it is clear that 𝛬 depends on the concentration with
deviations being greater the larger the concentration of the solution. This is interpreted
as indicating that such solutions cannot be considered as ideal, and that the variation in
𝛬 with concentration reflects increasing non-ideality as the concentration increases. This
non-ideality results from electrostatic interactions between the oppositely charged ions.

[Link]. Weak electrolytes

The conductivity  is again proportional to 𝑐𝑎𝑐𝑡𝑢𝑎𝑙 and

𝜅
Λm = (2.1.7)
𝑐𝑠𝑡𝑜𝑖𝑐ℎ

and so
𝑐𝑎𝑐𝑡𝑢𝑎𝑙
Λ= (2.1.9)
𝑐𝑠𝑡𝑜𝑖𝑐ℎ

But for a weak electrolyte:

𝑐𝑎𝑐𝑡𝑢𝑎𝑙 = 𝛼𝑐𝑠𝑡𝑜𝑖𝑐ℎ (2.1.12)

𝛼𝑐𝑠𝑡𝑜𝑖𝑐ℎ
∴Λ∝ ∝𝛼 (2.1.13)
𝑐𝑠𝑡𝑜𝑖𝑐ℎ

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Compiled by Dr Tlhabologo M Kabomo, Department of Chemistry, University of Botswana
Now 𝛼 is not constant over a range of concentration for a weak electrolyte. In particular,
the fraction ionised increases dramatically as the concentration decreases and tends to
zero. Hence for a weak electrolyte 𝛬 is expected to vary with stoichiometric concentration,
and in particular to increase dramatically with decrease in concentration to a limiting
value when 𝑐𝑠𝑡𝑜𝑖𝑐ℎ → 0. Thus, "less is more" for these oddities which possess the
remarkable ability to exhibit infinite conductivity at infinite dilution. Although Λ° cannot
be estimated by extrapolation, there is a clever work-around.

𝛼 = 1 when Λ = Λ° (2.1.14)

Therefore
Λ
𝛼= (2.1.15)
Λ°

Example 2.3 Molar conductivity for a weak electrolyte

At 25 C, the molar conductivity of a 4.00  10−3 mol dm−3 solution of Cl2CHCOOH is
359.0 S cm2 mol−1. If , the limiting molar conductivity, for Cl2CHCOOH is 385.0 S cm2
mol−1 , what is the fraction ionized at this concentration? From this calculate the
equilibrium concentrations of H3O+, Cl2CHCOO−(aq) and Cl2CHCOOH(aq), and from these
calculate the ionization constant for Cl2CHCOOH(aq).

Solution
𝛬 359.0 S cm2 mol−1
𝛼= = = 0.932
𝛬° 385.0 S cm2 mol−1

For
Cl2 CHCOOH(𝑎𝑞) ⇌ H3 O+ (𝑎𝑞) + Cl2 CHCOO− (𝑎𝑞)

[H3 O+ ]𝑎𝑐𝑡𝑢𝑎𝑙 [Cl2 CHCOO− ]𝑎𝑐𝑡𝑢𝑎𝑙

𝐾𝑎 = ( )
[Cl2 CHCOOH]𝑎𝑐𝑡𝑢𝑎𝑙
𝑒𝑞

But

[Cl2 CHCOOH]𝑠𝑡 = [Cl2 CHCOOH]𝑎𝑐 + [Cl2 CHCOO− ]𝑎𝑐

Also
[H3 O+ ]𝑎𝑐 = [Cl2 CHCOO− ]𝑎𝑐 = 𝛼[Cl2 CHCOOH]𝑠𝑡

[H3 O+ ]2𝑎𝑐𝑡𝑢𝑎𝑙
∴ 𝐾𝑎 = ( )
[Cl2 CHCOOH]𝑎𝑐𝑡𝑢𝑎𝑙
𝑒𝑞

[H3 O+ ]𝑎𝑐 = 𝛼[Cl2 CHCOOH]𝑠𝑡 = 0.932 × 4.00 × 10−3

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Compiled by Dr Tlhabologo M Kabomo, Department of Chemistry, University of Botswana
 [Cl2 CHCOOH]𝑎𝑐 = [Cl2 CHCOOH]𝑠𝑡 − [Cl2 CHCOO− ]𝑎𝑐

[Cl2 CHCOOH]𝑎𝑐 = 4.00 × 10−3 − 0.932 × 4.00 × 10−3

[Cl2 CHCOOH]𝑎𝑐 = 2.70 × 10−4

(3.73 × 10−3 )2
∴ 𝐾𝑎 = = 5.15 × 10−2 mol dm−3
2.70 × 10−4

2.2. Migration of dissolved ions in an electrostatic field

2.2.1. Independent migration of ions

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.

Table 2.1 Molar conductivities at infinite dilution for various salts

electrolyte Λ0 (25°C) difference electrolyte Λ0 (25°C) difference
KCl 149.9 HCl 426.2
LiCl 115.0 34.9 HNO3 421.1 4.9
KNO3 145.0 LiCl 115.0
LiNO3 140.1 34.9 LiNO3 110.1 4.9

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.

This principle is known as Kohlrausch's law of independent migration, which states that in
the limit of infinite dilution, each ion contributes a definite amount to the total molar
conductivity of the electrolyte irrespective of the nature of the electrolyte.

That is, for a symmetrical electrolyte, e.g. KCl

Λ° = 𝜆°+ + 𝜆°− (2.2.1)

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Compiled by Dr Tlhabologo M Kabomo, Department of Chemistry, University of Botswana
where 𝜆°+ is the molar conductivity of the cation, called the ionic molar conductivity and
𝜆°− is the molar conductivity of the anion.

For the unsymmetrical electrolyte AxBy, e.g. K2SO4(aq) which ionises give Ay+(aq) and Bx-
(aq) ions

Λ° = 𝑥𝜆°+ + 𝑦𝜆°− (2.2.2)

Example 2.4 Kohlrauch’s Law

The molar conductivity at 18 oC of a 0.0100 M aqueous solution of ammonia is
9.6 S cm2 mol−1 . For NH4Cl, the limiting molar conductivity is 129.8 S cm2 mol−1and the
molar ionic conductivities of OH− and Cl− are 174.0 and 65.6 S cm2 mol−1respectively.
Calculate Λ° for NH3 and the degree of ionization in 0.0100 M solution.

Solution
This is a question on Kohlrauch’s Law:

NH3 (𝑎𝑞) ⇌ NH4 + (𝑎𝑞) + OH − (𝑎𝑞)

So
Λ° (NH3 ) = 𝜆°NH + + 𝜆°OH−
4
But
Λ° (NH4 Cl) = 𝜆°NH + + 𝜆°Cl−
4

Therefore,
Λ° (NH3 ) = Λ° (NH4 Cl) + 𝜆°OH− − 𝜆°Cl−

Λ° (NH3 ) = (126.8 + 174.0 − 65.6) S cm2 mol−1

Λ° (NH3 ) = 238.2 S cm2 mol−1

The degree of ionization is:

Λ
α= °
Λ

9.6 S cm2 mol−1

α=
238.2 S cm2 mol−1

α = 0.040

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Compiled by Dr Tlhabologo M Kabomo, Department of Chemistry, University of Botswana
 2.2.2. Transport numbers
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 ions do not usually carry identical fractions of the charge.

The transport number of an ion is the fraction of the total current carried by the ion.

𝑡+ = fraction of current carried by cation

𝑡− = fraction of current carried by anion

The fractional character of the transport numbers implies that

𝑡+ + 𝑡− = 1 (2.2.3)

At infinite dilution,
Λ° = 𝜆°+ + 𝜆°− (2.2.4)

Since the transport numbers gives the fraction of the total current carried by each ion,
then

𝜆+ 𝜆−
𝑡+ = 𝑎𝑛𝑑 𝑡− = (2.2.5)
Λ Λ

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Compiled by Dr Tlhabologo M Kabomo, Department of Chemistry, University of Botswana
Example 2.5 Transport numbers
If the limiting molar conductivity for KCl(aq) at 25 C is 149.8 S cm2 mol−1 and the
limiting molar ionic conductivity for K+(aq) is 73.5 S cm2 mol−1, calculate the transport
number t+ for the K+ ion. What is the t− for Cl−(aq)? Comment on the values.

Solution
In the limit of infinite dilution:
°
𝜆°+ 𝜆°−
𝑡+ = ° 𝑎𝑛𝑑 𝑡−° = °
Λ Λ

73.5 S cm2 mol−1

𝑡+° = = 0.491
149. 5 S cm2 mol−1

∴ 𝑡−° = 1 − 𝑡+° = 1 − 0.491 = 0.591

Since the transport number for K+ is only slightly less than that for Cl−(aq), then the
fraction of the current carried by each other is fairly similar. This is reflected in the
limiting molar conductivities of each ion: 73.5 and 76.3 𝑆 𝑐𝑚2 𝑚𝑜𝑙 −1 for K+(aq) and
Cl−(aq) respectively.

2.3. Ostwald’s Dilution Law

Consider an electrolyte AB in solution

𝐴B ⇌ A+ + B − (2.3.1)

The equilibrium constant is given by

[A+ ][B− ]
𝐾𝑐 = (2.3.2)
[AB]

Suppose an amount of n moles of the electrolyte is present in a volume of V and that

the fraction dissociated in α, then:
𝐀𝐁 ⇌ 𝐀+ + 𝐁−
Amount present at equilibrium 𝑛(1 − 𝛼) 𝑛𝛼 𝑛𝛼

Concentration present at 𝑛(1 − 𝛼) 𝑛𝛼 𝑛𝛼

equilibrium 𝑉 𝑉 𝑉

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Compiled by Dr Tlhabologo M Kabomo, Department of Chemistry, University of Botswana
The equilibrium constant is given by
𝑛α 2
[A+ ][B− ] (V)
𝐾𝑐 = = (2.3.3)
[AB] n(1 − α)
V

𝑛2 α2
𝐾𝑐 = V2 (2.3.4)
𝑛(1 − α)
V

𝑛α2
𝐾𝑐 = (2.3.5)
𝑉(1 − α)

𝑛
Since 𝑉 = 𝑐, then

𝑐α2
𝐾𝑐 = (2.3.6)
1−α

Λ
But 𝛼 = Λ° , therefore

Λ 2
𝑐 ( °)
𝐾𝑐 = Λ (2.3.7)
Λ
1− °
Λ

𝑐Λ2
𝐾𝑐 = (2.3.8)
Λ° (Λ° − Λ)

2.4. Some applications of electrolytic conduction

Solubility products can be estimated from limiting ionic conductivities
Example 2.6 Solubility product of silver bromide
The conductivity of a saturated solution of silver bromide in water is 6.99  10−8 S
cm−1 at 18oC. If the molar ionic conductivities of Ag+(aq) and Br−(aq) are 53.5 and 68.0
S cm2 mol−1 respectively, find the solubility of silver bromide in water. From this
calculate the solubility product of silver bromide.

Solution
The limiting molar conductivity for AgBr is
32
Compiled by Dr Tlhabologo M Kabomo, Department of Chemistry, University of Botswana
 Λ° (AgBr(aq)) = λ°Ag+(aq) + λ°Br− (aq)

Λ° (AgBr(aq)) = (53.5 + 68.0)S cm2 mol−1

Λ° (AgBr(aq)) = 121.5 S cm2 mol−1

Since AgBr(s) is highly insoluble, then a saturated solution of AgBr(aq) will be a very
dilute solution of Ag+(aq) and Br−(aq) , and so

Λ = Λ° = 121.5 S cm2 mol−1

𝜅 = Λ° 𝑐𝑠𝑡𝑜𝑖𝑐ℎ

where 𝑐𝑠𝑡𝑜𝑖𝑐ℎ is here the concentration of the saturated solution of AgBr.

𝜅
𝑐𝑠𝑡𝑜𝑖𝑐ℎ =
𝛬°

6.99 × 10−8 S cm−1

𝑐𝑠𝑡𝑜𝑖𝑐ℎ =
121.5 S cm2 mol−1

𝑐𝑠𝑡𝑜𝑖𝑐ℎ = 5.75 × 10−10 mol cm−3

𝑐𝑠𝑡𝑜𝑖𝑐ℎ = 5.75 × 10−7 mol dm−3

Therefore, the solubility of AgBr in water is 5.75 × 10−7 mol dm−3 .

AgBr(𝑠) ⇌ Ag + (𝑎𝑞) + Br − (𝑎𝑞)

𝐾𝑠𝑝 = ([Ag + ][Br − ])𝑒𝑞

𝐾𝑠𝑝 = (5.75 × 10−7 mol dm−3 )2

𝐾𝑠𝑝 = 3.3 × 10−13 mol2 dm−6

33
Compiled by Dr Tlhabologo M Kabomo, Department of Chemistry, University of Botswana