University of Al-Ameed

College of Pharmacy

Physical pharmacy I
Electrolytes Solution

Lecture 7
2nd class, 1st semester
Dr. kamil Al-Tameemi
Contents
Introduction
Debye and Hückel theory
The Arrhenius theory
Theory of Electrolytic Dissociation
Properties of Solutions of Electrolytes
Activity versus concentration
Ionic Strength
Colligative Properties of Electrolytic Solutions
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Introduction
❑ The first satisfactory theory of ionic solutions was
that proposed by Arrhenius in 1887.

❑ The theory was based largely on studies of

I. Electric conductance by Kohlrausch,
II. Colligative properties by Van't Hoff, and
III. Chemical properties such as heats of neutralization
by Thomsen.
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➢ Although the theory proved quite useful for describing weak
electrolytes,

➢ it was soon found unsatisfactory for strong and moderately

strong electrolytes.

➢ Accordingly, many attempts were made to modify or replace

Arrhenius's ideas with better ones, and finally, in 1923, Debye
and Hückel put forth a new theory.

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Debye and Hückel theory:-

is based on the principles that

✓ Strong electrolytes are completely dissociated into ions in
solutions of moderate concentration and
✓ That any deviation from complete dissociation is due to
interionic attractions.

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 The Arrhenius Theory
✓ When electrolytes are dissolved in water,
✓ the solute exists in the form of ions in the solution, as seen in the
following equations:
Na+Cl- + H2O Na+ + Cl- + H2O (strong electrolyte)

HCl + H2O H3O+ + Cl- (strong electrolyte)

CH3COOH + H2O CH3COO-+ H3O+ (weak electrolyte)

Theory of Electrolytic Dissociation

❑The original Arrhenius theory, together with the alterations that have come
about as a result of the intensive research on electrolytes, is summarized as
follows.

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 Na+Cl- + H2O Na+ + Cl- + H2O (strong electrolyte)
❑ The solid form of Sodium Chloride is marked with plus and minus signs in reaction to
indicate that sodium chloride exists as ions even in the crystalline state.
❑ If electrodes are connected to a source of current and are placed in a mass of fused
Sodium Chloride, the molten compound will conduct the electric current because the
crystal lattice of the pure salt consists of ions.
❑ The addition of water to the solid dissolves the crystal and separates the ions in
solution.

HCl + H2O H3O+ + Cl- (strong electrolyte)

❖ Hydrogen Chloride exists essentially as neutral molecules rather than as ions in the
pure form and does not conduct electricity.
❖ When it reacts with water, however, it ionizes according to above reaction. H3O+ is the
modern representation of the hydrogen ion in water and is known as the hydronium
or oxonium ion.
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 CH3COOH + H2O CH3COO-+ H3O+ (weak electrolyte)

Acetic acid is a weak electrolyte, the oppositely directed arrows in equation indicating
that equilibrium between the molecules and the ions is established.

✓Some drugs such as anionic & cationic antibacterial & antiprotozoal agents
are more active when in ionic state.
✓Other compounds such as hydroxybenzoate ester (paraben preservative)
& general anesthetics bring about their biological action as a non electrolyte,
✓Still other compounds as Sulfonamides are exert their action both as ions &
as neutral molecule.

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Properties of Solutions of Electrolytes
Electrolysis
➢ When, under a potential of several volts, a direct electric current (dc) flows through an
electrolytic cell (Fig. bellow), a chemical reaction occurs.
➢ The process is known as electrolysis. Electrons enter the cell from the battery or
generator at the cathode (road down);
➢ they combine with positive ions or cations in the solution, and the cations are
accordingly reduced.
✓ The negative ions, or anions, carry electrons through the solution and discharge them
at the anode (road up), and the anions are accordingly oxidized.

❑ The current in a solution consists of a flow of positive and negative ions toward the
electrodes,
❑ whereas the current in a metallic conductor consists of a flow of free electrons
migrating through a crystal lattice of fixed positive ions.
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Reduction :-
✓ occurs at the cathode, where
electrons enter from the
external circuit and are added
to a chemical species in
solution ( cations).

Oxidation :-
➢ occurs at the anode, where
the electrons are removed
from a chemical species in
solution (anions) and go into
the external circuit.
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 Activity versus concentration

✓ The oppositely charged ions in solution of strong electrolytes

influences one another through interionic attractive forces.
✓ Although this interference is negligible in dilute solutions, it
becomes appreciable at higher concentrations.

❑ In solutions of weak electrolytes, the number of ions is small and

the interionic attraction insignificant.
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➢ The ions can associate at high concentration into groups known
as ion pairs (e.g., Na+Cl-) and ion triplets (Na+Cl-Na+).
➢ In other ward, the ions are not free in solution but founds as
groups bind together.

oBecause of the interionic attraction, the electrical conductivity

will be less than usual.
oSimilarly, the values of the freezing point depression and the
other colligative properties are less than expected for solutions
of free ions.
oConsequently, a strong electrolyte may be completely ionized,
yet incompletely dissociated into free ions.
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❑ Therefore, the concentration of strong electrolytes may cause
misleading and one should use what is called activity instead of
concentration.

The activity is less than the actual concentration of the solute, not
because the strong electrolyte is only partly ionized, but rather
because some of the ions are effectively “taken out of the solution”
by the interionic attractive forces.
At infinite dilution (i.e., very dilute solution of less than 0.01
M), in which the ions are so widely separated that they do
not interact with one another,
✓ the activity of an ion is equal to its concentration.
✓ As the concentration is increased, the activity of the ions
becomes less than the molar concentration.

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As the concentrations of some of the
electrolytes are increased:-
The curves pass through minima and rise
again to values greater than unity. Why?

❑ The initial decrease in the activity

coefficient with increasing concentration
is due to the interionic attraction.

➢ The rise in the activity coefficient following

the minimum in the curve of an electrolyte,
such as HCl and CaCl2, can be attributed to
the attraction of the water molecules for
the ions in concentrated aqueous solution.
➢ This solvation reduces the interionic
attractions and increases the activity
coefficient of the solute.
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 Ionic Strength
❑ To calculate the activities of solutions, the scientists Debye - Hückel
introduce the concept of ionic strength (µ).

❑ It is a characteristic of an electrolyte solution ,

❑ it is a measure of the intensity of the electrical field in a solution or
the concentration of ions in that solution.
❑ ionic strength (µ) which is a mathematical expression that describes
the interionic forces of the ions in a solution.
The ionic strength can be calculated as:
µ = 0.5 [(C1 Z12) + (C2 Z22) + (C3 Z32)] + ….. etc.
where:
C is molar concentration
Z is valence

The ionic strength depends on the total number of ionic charges

and not on the specific properties or chemical nature of the solute
in solution.

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 Example 1: What is the ionic strength of:
(a) 0.01 M KCl solution
(b) 0.01 M BaSO4 solution
(c) 0.01 M Na2SO4 solution
(d) a solution containing all of these 3 salts.
Answer:
(a) µ = 0.5 [(0.01 × 12) + (0.01 × 12)] = 0.01
(b) µ = 0.5 [(0.01 × 22) + (0.01 × 22)] = 0.04
(c) µ = 0.5 [(0.02 × 12) + (0.01 × 22)] = 0.03
(d) µtotal = sum of ionic strength of all the compounds
= 0.01 + 0.04 + 0.03 = 0.08
Note that all solutions have the same concentration but
they differ in µ.
It is observed in this example that the ionic strength:-

✓ µ of a 1:1 electrolyte such as KCl is the same as the

concentration;
✓ µ of a 1:2 electrolyte such as Na2SO4 is three times
the concentration; and
✓ µ for a 2:2 electrolyte is four times the
concentration.
To calculate activity, Debye-Hückel introduce the following
equations:
(𝒛+)(𝒛−)√𝝁
Log ɣ± = −𝟎. 𝟓𝟏
𝟏 + √𝝁

❑ (0.51 )this constant present in equation depends on the

temperature of water used to make the solution at 25 °C.

❑ z – Charge number.
Example: Calculate the activity coefficient of a 0.09 M solution of
sodium phenobarbital which has an ionic strength of 0.09

(𝑧+)(𝑧−)√𝜇
Log ɣ± = −0.51
1 + √𝜇

ɣ± = 0.76
This means that only 76% of the ions are free, while the other 24%
are in groups (ion pairs).
Osmolality
Although osmotic pressure classically is given in atmospheres,
➢ In clinical practice it is expressed in terms of osmols (Osm) or
milliosmols (mOsm).

➢ A solution containing a ( 1 m solution) is referred to as a 1-osmolal

solution. It contains 1 osmol (Osm) or 1000 milliosmols (mOsm) of
solute per kilogram of solvent.
➢ Osmolality measures the total number of particles dissolved in1 kg
of water, and depends on the electrolytic nature of the solute.
however, owing to their ionic interactions.
✓ The apparent number of “particles” in solution, as measured by osmometry or one
of the other colligative methods, will depend on the extent of these interactions.
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✓ An un-ionized material (i.e., a nonelectrolyte) is used as the reference solute for
osmolality measurements,
✓ For an electrolyte that dissociates into ions in a dilute solution, osmolality or
milliosmolality can be calculated from

𝐦𝐎𝐬𝐦
𝐌𝐢𝐥𝐥𝐢𝐨𝐬𝐦𝐨𝐥𝐚𝐥𝐢𝐭𝐲 = 𝐢 × 𝐦𝐦
𝐤𝐠

where
i is approximately the number of ions formed per molecule and mm is the millimolal
concentration.
➢ If no ionic interactions occurred in a solution of sodium chloride, i would equal 2.0.
➢ In a typical case, for a 1:1 electrolyte in dilute solution, i is approximately 1.86 rather
than 2.0, owing to ionic interaction between the positively and negatively charged ions.

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Colligative Properties of Electrolytic Solutions

❑ Van't Hoff found, however, that solutions of electrolytes ( of the same

concentration) gave osmotic pressures approximately two, three, and more times
larger than expected from this equation,
❑ depending on the electrolyte investigated.
Introducing a correction factor i to account for the irrational behavior of ionic
solutions, and in this case
π = iRTc
By the use of this equation, Van't Hoff was able to obtain:-
❖ A calculated values that compared favorably with the experimental results of osmotic
pressure.
Van't Hoff recognized that i approached the number of ions into which the molecule
dissociated as the solution was made increasingly dilute.

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