Physical Pharmacy 3 PDF

‫المرحلة الثانية‬
‫‪Physical pharmacy – 1 st semester‬‬
‫المحاضرة الثالثة‬
‫د‪ .‬رشا خلف‬
Elelectrolyte solution:
 Colligative Properties of Electrolytic Solutions and

Concentrated Solutions of Nonelectrolytes:
van’t Hoff observed that the osmotic pressure,π, of dilute solutions of

nonelectrolytes, such as sucrose and urea, could be expressed by the
equation π = RTc
solutions of electrolytes 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 behavior of ionic solutions.
π = iRTc
By the use of this equation, van’t Hoff was able to obtain calculated values that
compared favorably with the experimental results of osmotic pressure.
i approached the number of ions into which the molecule dissociated
2 for NaCl and CaSO4

3 for K2SO4 and CaCl2
4 for FeCl3.
The colligative properties in dilute solutions of electrolytes are expressed on the

molal scale by the equations
Ex : calculate the boiling point of a 0.250 m aquous solution of
iron(III) chloride at 1.00 atm ( kb= 0.512 ◦C m-1).
Ex : if 5g of a strong electrolyte NaoH (Mwt= 40 g\mole) is added to 100 g

of water at 25 ◦C . the vapor pressure of pure water is 23.8 mmHg.
Calculate the vapor pressure ,B.P, F.P of the solution and compare your
results with that of a solution containing 22.5 g of glucose (Mwt= 180.16
g\mole) in 100 g of water at 25 ◦C.
Drugs and Ionization
Some drugs, such as anionic and cationic antibacterial and antiprotozoal agents,
are more active when in the ionic state.
Other compounds, such as the hydroxybenzoate esters (parabens) and many general anesthetics,
bring about their biologic effects as nonelectrolytes.
Still other compounds, such as the sulfonamides,
are thought to exert their drug action both as ions and as neutral molecules
According to Arrhenius theory used α to express the degree of dissociation of

both strong and weak electrolytes, and van’t Hoff introduced
the factor i to account for the deviation of strong and weak electrolytes
Activity (a) and Activity Coefficients(γ)
In strong electrolytes solutions The large number of oppositely charged ions

in solutions of electrolytes influence one another through interionic
attractive forces and also associate at high concentration into groups known
as ion pairs (e.g., Na+Cl-) and ion triplets (Na+Cl-Na+).
So ions are not completely dissociated from each other and do not exert their
full effect i.e : i less than 2
Because of interionic attractive forces and ion association , in moderatly

concentrated solutions of strong electrolytes , the value of the freezing point
depression and other Collegiative properties are less than expected for
solutions of unhindered free ions
•Consequently, a strong electrolyte may be completely ionized, yet

incompletely dissociated into free ions.
Ex : the osmotic pressure of a 2.0 m solution of sodium chloride
at 20◦C is 91.3 atm, what is the theoretical I factor and what is the
calculated i factor.
Ex: the freezing point depression of a solution containing 4 g of an electrolyte
(methapyriflene Hcl) in 100 g. solution was a 0.423 c . (methapyriflene Hcl)
dissociated into two ions and has a Mwt of 297.85 . what is the expected i factor ?.
and calculated i factor / what do you expect from this values?
One may think of the solution as having an “effective concentration” or, as it is
called, an activity. The activity, in general, is less than the actual or
stoichiometric 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 play” by the electrostatic forces of interaction.
At infinite dilution, in which the ions are so widely separated that they do not
interact with one another, the activity a of an ion is equal to its concentration,
expressed as molality or molarity. It is written on a molal basis at infinite
dilution as
a= m or
As the concentration of the solution is increased, the ratio becomes less than
unity because the effective concentration or activity of the ions becomes less
than the stoichiometric or molal concentration. This ratio is known as the
practical activity coefficient, γm, on the molal scale, and the formula is written,
for a particular ionic species, as
Debye and H¨uckel theory

a theoretical method by which it is possible to calculate the activity
coefficient of a single ion as well as the mean ionic activity coefficient
of a solute without recourse to experimental data. Although the
theoretical equation agrees with experimental findings only in dilute
solutions.
The Debye-Hückel theory is based on three assumptions of how ions

act in solution:
1. Electrolytes completely dissociate into ions in solution.

2. Solutions of Electrolytes are very dilute, on the order of 0.01 M.
The mean values of for NaCl, CaCl2, andZnSO4 are plotted against
the square root of the molality. The reason for plotting the square root
of the concentration is due to the form that the Debye–H¨uckel
equation takes.
 the activity coefficient approaches unity with increasing

dilution
 As the concentrations of some of the electrolytes are

increased, their curves pass through minima and rise again to
values greater than unity?????
The initial decrease in the activity coefficient with increasing

concentration is due to the interionic attraction, which causes the
activity to be less than the stoichiometric concentration. 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.
Activity of the Solvent
to define the activity of the solvent on the mole fraction scale.
When a solution is made infinitely dilute , therefore, X1= 1,
and the solvent behaves ideally in conformity with Raoult’s
law. Under this condition, the mole fraction can be set equal to
the activity of the solvent, or
a = X1 = 1
As the solution becomes more concentrated in solute, the activity of
the solvent ordinarily becomes less than the mole fraction
concentration, and the ratio can be given, as for the solute, by the
rational activity coefficient,
The activity of a volatile solvent can be determined rather simply. The

ratio of the vapor pressure, p1, of the solvent in a solution to the vapor
pressure of pure solvent, p1◦, is approximately equal to the activity of
the solvent at ordinary pressures: a1 = p1/p◦.
Calculating Escaping Tendency
The vapor pressure of water in a solution containing 0.5 mole of
sucrose in 1000 g of water is 17.38 mm and the vapor pressure of
pure water at 20◦C is 17.54 mm. What is the activity (or escaping
tendency) of water in the solution?
Ex: the vapor pressure of pure water at 25 ◦C IS 23.8 mmHg
a- Compute the lowering of vapor pressure of water when 25g
of CaCl2 (Mwt= 110.99 g\mole) is added to 100g of water
b- Compute the activity and activity coefficient of water in the
solution

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‫المرحلة الثانية‬

‫‪Physical pharmacy – 1 st semester‬‬

 Colligative Properties of Electrolytic Solutions and

van’t Hoff observed that the osmotic pressure,π, of dilute solutions of

i approached the number of ions into which the molecule dissociated

2 for NaCl and CaSO4

The colligative properties in dilute solutions of electrolytes are expressed on the

Ex : if 5g of a strong electrolyte NaoH (Mwt= 40 g\mole) is added to 100 g

According to Arrhenius theory used α to express the degree of dissociation of

Activity (a) and Activity Coefficients(γ)

In strong electrolytes solutions The large number of oppositely charged ions

Because of interionic attractive forces and ion association , in moderatly

•Consequently, a strong electrolyte may be completely ionized, yet

Debye and H¨uckel theory

The Debye-Hückel theory is based on three assumptions of how ions

1. Electrolytes completely dissociate into ions in solution.

 the activity coefficient approaches unity with increasing

 As the concentrations of some of the electrolytes are

The initial decrease in the activity coefficient with increasing

The activity of a volatile solvent can be determined rather simply. The

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