KENYATTA UNIVERSITY

SCHOOL OF PURE AND APPLIED SCIENCES

DEPARTMENT OF CHEMISTRY

SCH 403 PHASE EQUILIBRIA

Series -3 (Colligative Properties)

Dr. Eric Masika

Physical Chemistry and Nanotechnology
Office: Biochemistry – Room 31

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 Course Objective: Second Semester 2014/15
To provide:
 Definitions and basic concepts of phase equilibria. Application of
Clausius-Clapeyron equation, calculating phase diagrams for
different systems from fundamental thermodynamic properties;
changes in enthalpy and volume accompanying phase transitions.
 Phase rule of one component and binary system. Phase equilibria:
liquid/vapour, liquid/liquid and solid/liquid systems, including
compound formation. Vapour pressure composition diagrams for
liquid mixtures. This will include Interpretation of equilibrium
phase diagrams.
 Colligative properties: Explain how the amount of an electrolytic or
nonelectrolytic solute affects the freezing point, boiling point, and
osmotic pressure of a solvent; and perform calculations involving
these colligative properties including determination of molar mass

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 Course Content: Second Semester 2014/15
Covers:
 Definitions and basic concepts of phase equilibria. Derivation and
application of Clausius-Clapeyron equation.

 Phase rule of one component and binary system. Phase equilibria:

liquid/vapour, liquid/liquid and solid/liquid systems, including
compound formation. Vapour pressure composition diagrams for
liquid mixtures.
 Colligative properties: Vapor Pressure Lowering (Raoults Law)
Freezing Point Depression / Boiling Point Elevation and Osmotic
Pressure.
Experimental work:
•Practicals on phase equilibria and colligative properties

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 Methodology and Assessment
Methodology:
Lectures, tutorials and THREE selected practical.

Assessment:
Continuous assessment (30%) will include assignments, written
tests and laboratory reports. One 2 hour paper at the end of
semester will constitute 70%

Date for Diary :

CAT 1: Scheduled for 11th February 2015 at 5:00 pm

CAT 2: Scheduled for 18th March 2015 at 5:00 pm

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 References:
Suggested Reading:
1. Atkins, P.W., Physical Chemistry, 8th Edition, OUP

2. Gordon M Barrow, Physical Chemistry, McGraw-Hill Education

(India) Pvt Ltd

3. Atkins P. and Jones L., Chemical Principles; The Quest for Insight,
2nd Edition, USA

4. Any Advanced Physical Chemistry Book

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 Definitions: Colligative Properties
Definition:
Colligative properties refer to physical properties of solutions that
depend more directly on the concentration of the solvent. These
properties include:
 Lowering of vapour pressure
 The freezing point
 The boiling point
 The osmotic pressure
Since the three are tied ‘together’ (Latin: co ligare); they are referred
to as colligative properties of solutions.
Thus the colligative properties really depend on the escaping tendency of
solvent molecules from the liquid phase. Therefore, the vapour pressure is a
direct measure of escaping tendency, so we can use these terms more or less
interchangeably.
The tendency of molecules to escape from a liquid phase into the gas phase
depends in part on how much of an increase in entropy can be achieved in
doing so. 6
Concept Map Colligative Properties

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http://www.chem1.com/acad/virtualtextbook.html
 General Properties of Solutions
1. A solution is a homogeneous mixture of two or more
components.
2. It has variable composition.
3. The dissolved solute is molecular or ionic in size.
4. A solution may be either colored or colorless nut is generally
transparent.
5. The solute remains uniformly distributed throughout the
solution and will not settle out through time.
6. The solute can be separated from the solvent by physical
methods.

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 Effect of Solutes on Properties of Solutions
• Reduces the vapor pressure of the solvent in the solution.
• Lowers the freezing point of the solution.
• Raises the boiling point of the solution

Effect of Vapour Pressure

 Vapour pressure of the
solvent in a solution is
decreased by the
solute.
 The more solute is
present, the more the
vapor pressure of the
water is lowered.
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 Effect of Vapour Pressure (Schematic illustration)
Lower vapor
Higher vapor pressure
pressure

Solution containing Solute particle

Pure solvent Solvent particle nonvolatile solute
 Note that on the surface of the pure solvent (shown on the
left) there are more solvent molecules at the surface than
in the right-hand solution flask.
 Thus, it is more likely that solvent molecules escape into
the gas phase on the left than on the right. Which implies
that the solution should have a lower vapor pressure than
the pure solvent.
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Effect of Vapour Pressure (Worked example)

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 Freezing Point Depression
 The freezing point of a substance is the temperature at
which the solid and liquid forms can coexist indefinitely
— that is, they are in equilibrium. Under these conditions
molecules pass between the two phases at equal rates
because their escaping tendencies from the two phases are
identical.

 Adding solutes to freezing liquids (like salt to water)

lowers the freezing point.
Reason:
For Freezing Point Depression: solute molecules get in the
way of the formation of crystals. In essence, the connections
that need to be made are harder to create, so lower
temperature is required.
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Freezing Point Depression (cont.)

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Effect Freezing Point (Graphical representation)

A B

 Note the enhanced decrease in the freezing

normal value compared to the increase
point.
 While in Fig B, the P-T of the solve
nonvolatile solute system showing depressi
point and elevation of boiling point. 14
 Effect on Freezing Point (Application)
I. The freezing-point depression of
aqueous solutions plays an
important role in helping keep
travelers safe in cold, icy weather.
• The truck spreads a layer of salt on the
icy road to make the ice melt.
• The melted ice forms a solution with a
lower freezing point than that of pure
water.

II. Antifreeze is added to a car’s

cooling system to keep it from
freezing and damaging the
engine when the temperature
falls below freezing. 15
 Boiling-Point Elevation
 If addition of a nonvolatile solute lowers the vapor pressure of
the solution, then it follows that the temperature must be raised
to restore the vapor pressure to the value corresponding to the
pure solvent.
 In particular, the temperature at which the vapor pressure is 1
atm will be higher than the normal boiling point by an amount
known as the boiling point elevation.

Reason:
For the Boiling Point Elevation: think of the solute molecules
interfering with the liquid’s ability to become a gas. They get in the
way… so need more energy to overcome resulting in higher
temperature.

(Cf. with earlier graphical representation).

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Boiling-Point Elevation

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 Boiling-Point Elevation ( Examples: constants)
solvent normal bp, °C Kb , K mori kg

water 100 0.514

ethanol 79 1.19
acetic acid 118 2.93
carbon tetrachloride 76.5 5.03

Question:
Sucrose (C22011H22, 342 g mol-1), like many sugars, is highly
soluble in water; almost 2000 g will dissolve in 1 L of water,
giving rise to what amounts to pancake syrup. Estimate the boiling
point of such a sugar solution.

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 Boiling-Point Elevation (Application)
Utilize both a solute and
pressure to raise the boiling
point of water to prevent
“boiling over”.

Pressure cap keeps pressure

inside cooling system above 1
atm, raising the boiling point.

In addition, ethylene glycol is

used as a solute to raise the
boiling point.

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 Osmotic pressure
Osmosis refers to the flow of solvent
molecules past a semipermeable
membrane that stops the flow of solute
molecules only. When a solution and
the pure solvent are placed on either
side of a semipermeable membrane, it
is found that more solvent molecules
flow out of the pure solvent side of the
membrane than solvent flows into the
pure solvent from the solution side.
This is because more solvent molecules
are at the membrane interface on the
solvent side of the membrane than on
the solution side.
Therefore, it is more likely that a
solvent molecule will pass from the
solvent side to the solution side than
vice versa. That difference in flow rate
causes the osmotic pressure of the
solution to rise. 20
 Concentration and Colligative Properties
 Three colligative properties set equal to three different
concentrations terms times a solvent constant

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 The Van’t Hoff Factor
Very simply, Van’t Hoff corrects for the fact that the number of
particles you throw into solution is not always the number of
particles that determine the magnitude of the property. For example,
think about what happens when you put the following one mole
quantities into a liter of water. Which one raises the boiling point
the most?
1. 1 mole NaCl 2. 1 mole Na2S 3. 1 mole CaS 4. 1 mole sugar

1 mole Na+ 0 moles

2 moles Na+ 1 mole
and 1 mole CaS
1 mole S2− sugar
Cl − insoluble

Van’t Hoff factor, which is i = 2, 3, 0 and 1, respectively for the four

solutions. i is simply inserted into every colligative property equation
to make the correction. The Van't Hoff factor is 1 for all non-
electrolyte solutes and equals the total number of ions released for
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electrolytes.
The Van’t Hoff Factor (Example)

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 SAQ
1. Estimate the freezing point of an antifreeze mixture is made up
by combining one volume of ethylene glycol (MW = 62, density
1.11 g cm-3) with two volumes of water.

2. Excluding any possible chemical reactions, which would be

more effective as an antifreeze; a solution containing 25 m
methyl alcohol (CH3OH) or 25 m KCl?

3. You have 500 mL of 1M solutions of NaCl, Na2SO4, Na3PO4, and

Al2(SO4)3. Which solution will have the highest boiling point?

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 Summary
Adding a solute to a solvent:
• Decreases the vapor pressure of the solvent
• Decreases the freezing point of the solution
• Increases the Boiling point of the solution
• The properties listed above depend on the concentration
of the solute particles, not what the particles are.
Key Words:
•Breezing-point depression: the difference in temperature
between the freezing point of a solution and the freezing
point of the pure solvent
•Boiling-point elevation: the difference in temperature
between the boiling point of a solution and the boiling
point of the pure solvent 25