BACHELOR OF SCIENCE IN PHARMACY:

PHYSICAL PHARMACY

Topic: Colligative Properties

Expected Outcomes:
At the end of this unit, the students are expected to:
 Understand the physical properties necessary to define a system
 Enumerate the different colligative properties and its principle
 Gain knowledge involving problems in Colligative Properties

Required Readings:
Sinko, P.J., Martin’s Physical Pharmacy and Pharmaceutical Sciences. Philadelphia, PA : Wolters
Kluwer. 2017
Smith, B. Remington Education: Physical Pharmacy. London :Pharmaceutical Press. 2016
Kumar, D. S. ) Applied thermodynamics. S. K. Kataria & Sons. 2017
Helmer, Erica Drug design and medicinal chemistry Callisto Reference. 2015
Atkins Elements of Physical Chemistry. 2017

Notes:
Physical Properties of Substances
1. Colligative Properties-depend mainly on the number of particles in a solution.
 Osmotic Pressure, Vapor Pressure Lowering, Freezing Point Depression, Boiling Point
Elevation.
2. Additive Properties-depend on the total contribution of the atoms in the molecule or on the
sum of the properties of the constituents in a solution.
 Molecular Weight
3. Constitutive Properties-depend on the arrangement and to a lesser extent on the number
and kind of atoms within a molecule
 Refractive Index, Optical Rotation, Solubility
Colligative Properties
On adding a solute to a solvent, the properties of the solvent are modified.
Vapor pressure decreases
Freezing point decreases
Boiling point increases
Osmosis is possible (osmotic pressure)
 These changes are called COLLIGATIVE PROPERTIES.
 They depend only on the NUMBER of solute particles relative to solvent particles,
not on the KIND of solute particles.

Vapor Pressure
 is the pressure of the saturated vapor above a liquid resulting from the escape of the
surface liquid.
 the vapor pressure of an ideal solution is dependent on the vapor pressure of each
chemical component and the mole fraction of the component present in the solution.
 When a nonvolatile solute is combined with a volatile solvent, the vapor above the solution
is provided solely by the solvent.
 The solute reduces the escaping tendency of the solvent, and, on the basis of Raoult’s Law.

Raoult’s Law
 The vapor pressure of a solution containing a nonvolatile solute is lowered proportional to
the relative number of the solute molecules.

Lowering of the Vapor Pressure

 According to Raoult’s Law, the vapor pressure of a solvent over a dilute solution is equal to
the vapor pressure of the pure solvent, times the mole fraction of solute in the solution .
 Determination of the Vapor Pressure of Solution
 Manometer is used and the difference of the vapor pressure between the solution and the
pure solvent.
 For dilute aqueous solutions, however, the vapor pressure lowering is so slight as to
produce a serious error in the measurement.
 Accurate differential manometers: small differences in vapor pressure.
 The isopiestic method is used frequently for the precise determination of vapor pressures.

Boiling Point
 Is the temperature at which the vapor pressure of the liquid becomes equal to the external
atmospheric pressure

Elevation of the Boiling Point

 The boiling point of a solution of a nonvolatile solute is higher than that of the pure solvent,
(solute lowers the vapor pressure of the solvent).
Determination of Boiling Point Elevation
 In the Cottrell boiling point apparatus, the vapor and the boiling solvent are pumped by the
force of ebullition through a glass tube and sprayed over the thermometer bulb to obtain an
invariant equilibrium temperature.

Boiling Point
 the phenomenon that the boiling point of a liquid (a solvent) will be higher when another
compound is added, meaning that a solution has a higher boiling point than a pure solvent.
 This happens whenever a non-volatile solute, such as a salt, is added to a pure solvent,
such as water.
 The boiling point can be measured accurately using an ebullioscope.

Freezing Point
 the phenomenon in which the freezing point of a liquid (a solvent) is depressed when
another compound is added, meaning that a solution has a lower freezing point than a
pure solvent.
 This happens whenever a non-volatile solute is added to a pure solvent, such as water.
 The phenomenon may be observed in sea water, which due to its salt content remains
liquid at temperatures below 0°C (32°F), the freezing point of pure water.
 The triple point of air-free water, at which solid, liquid, and vapor are in equilibrium, lies at a
pressure of 4.58 mm Hg and a temperature of 0.0098 °C.
 If a solute is dissolved in the liquid at the triple point, the escaping tendency or vapor
pressure of the liquid solvent is lowered below that of pure solid solvent.
 The temperature must drop in order to reestablish equilibrium between the liquid and the
solid.

Methods for the Determination of Freezing Point Lowering

1. Beckmann method
2. The Equilibrium method.

Beckmann method
 It consists of a jacketed tube with a sidearm through which the test material may be
introduced. A Beckmann thermometer is supported in the tube and extends into the test
solution.
 A glass stirrer passes through a tube in the stopper and is operated manually or by means
of a motor.
 The tube and jacket are supported in a vessel containing mixture of salt and ice.
 In carrying out a determination, the temperature is read on the Beckmann differential
thermometer at the freezing point of the pure solvent, water.
 A known weight of the solute is introduced into the apparatus, containing a given weight of
solvent, and the freezing point of the solution is read and recorded.
Change in Freezing Point
 The freezing point of a solution is LOWER than that of the pure solvent

Computations
1.60 g of naphthalene (C10H8) is dissolved in 20.0 g of benzene. The freezing point of pure
benzene is 5.5 oC, and the freezing point of the mixture is 2.8 oC. What is the molal freezing point
depression constant, Kf of benzene?
Strategy:

Step 1: Calculate the freezing point depression of benzene.

Tf = (Freezing point of pure solvent) - (Freezing point of solution)
(5.5 oC) - (2.8 oC) = 2.7 oC

Step 2 : Calculate the molal concentration of the solution.

molality = moles of solute / kg of solvent
moles of naphthalene = (1.60 g) (1 mol / 128 g) = 0.0125 mol naphthalene
molality of solution = (0.0125 mol) / (0.0200 kg) = 0.625 m

Step 3: Calculate Kf of the solution.

Tf = (Kf) (m)

(2.7 oC) = (Kf) (0.625 m)

Kf = 4.3 oC/m

Osmotic pressure
 is the pressure which needs to be applied to a solution to prevent the inward flow of water
across a semipermeable membrane.
 The phenomenon of osmotic pressure arises from the tendency of a pure solvent to move
through a semi-permeable membrane and into a solution containing a solute to which the
membrane is impermeable.
 All aqueous solutions of non-volatile solutes exert an osmotic pressure.
 Osmosis is the diffusion of solvent through a semi-permeable membrane that allows only
solvent to move through it.
 Osmotic Potential is the opposite of water potential, which is the degree to which a solvent
tends to stay in a liquid.
 Osmotic Pressure Osmometer is based on the principle of thistle tube.

Van’t Hoff Equation

¶V= Nrt or ¶=mRT
Where:
¶ is the osmotic pressure in atm
V is the volume of solutions in Liters
n is the number of moles of solute
R is the gas constant equal to 0.082L atm/mole
T is the absolute temperature

Van’t Hoff concluded that there was an apparent analogy between solutions and gases and that
the osmotic pressure in a dilute solution was equal to the pressure that the solute would exert if it
were a gas occupying volume.
Corresponded to the equation for ideal gas.

Morse Equation
¶= RTm
 Osmotic pressure is an important factor affecting cells. Osmoregulation is the homeostasis
mechanism of an organism to reach balance in osmotic pressure.
 Hypertonicity is the presence of a solution that causes cells to shrink.
 Hypotonicity is the presence of a solution that causes cells to swell.
 Isotonic is the presence of a solution that produces no change in cell volume.

COLLIGATIVE PROPERTIES COMPUTATIONS

If 0.340 mole of non-volatile non-electrolyte are dissolved in 2.67 mole of water, what is the VP of
the resulting solution? The VP of pure water is 13.8 mmHg at 25 degC.
Tb = Kb(m)
= (Kb) (1000)(W2)
(W1)(MW2)
BPSOLN = BPSOLVENT + BPE
BPSOLN = 100degC + ((1)(Kb)(m))
BPSOLN = 100degC + ((1)(Kb)(wtsolute/Mwsolute/Kgsolvent))
FPSOLN = FPSOLVENT – FPD
FPSOLN = 0degC –((1)(1.86degC/molal)(m))
FPSOLN = 0degC –((1)(1.86degC/molal))(wtsolute/Mwsolute/Kgsolvent))

What would be the bp elevation of a 0.05m of soln. of KCl?

Kb of H2O= 0.52degC

What is bp of a soln. containing 50g dextrose (MW= 180) in 1000mL of water?

Kb= 0.52 degC/mole

An amount of NaCl equal to 31.65 g is added to 220 mL of water at 37 deg C. Assuming complete
dissociation of NaCl in water, compute for the boiling point of the salt solution.
What is the freezing point of a solution of ethyl alcohol that contains 20 g of solute C2H5OH
dissolved in 590 g of water.

What is the osmotic pressure of a solution prepared by adding 13.65 g of sucrose C12H22O11 to
enough water to make 250 mL of solution at 25 deg C?