Physical

Chemistry I
(CHY2018)
Unit 1: Phase Equilibria

Prepared by: Dr. A. Redway

Modified by: Ms. L. Scarlet1
 Course Information
Get course material at utechonline.utech.edu.jm or Scoology.com (access code: 4RDC-F4TD-C9475)

Assessment
• Test 1 Week 6 15%
• Test 2 Week 12 15%
• Tutorial quizzes 20%
• Laboratory 20%
• Final examination 30%
2
At the end of the unit, students
should be able to:
• Review the colligative • Raoult’s Law as applied to
properties of solution the vapour pressures of
miscible liquids
• Theory of Ideal Solutions
• Understand one component • Phase diagrams and
fractional distillation,
systems: vapour pressure
azeotropic mixtures and
diagrams.
eutectic systems.
• The qualitative relationship
between boiling point, latent
• Partition coefficients -
immiscible Solutions
heat of Vaporization and
intermolecular forces.
• Two component systems - Recommended text:
3
mixtures of two liquids
Elements of Physical Chemistry
(miscible).
(5th) – by Peter Atkins
 What is Phase Equilibria?

The study of the equilibrium which exists between or within different states of matter
namely solid, liquid and gas.

4
 Colligative Properties of
solution
• Colligative properties of solutions are properties that depend upon the
concentration of solute molecules or ions, but not upon the identity of the solute.
• In liquid solutions, the solute molecules displace some solvent molecules and so
reduce the concentration of solvent.
• Colligative properties depend only on the ratio of solute to solvent molecules and
not on the properties of the solvent or solute
• Colligative properties are independent of the nature of the solute.
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 Colligative Properties of
solution
• ‘Colligative’ denotes ‘depending on the collection’.
• The properties are associated with changes in the entropy or disorder of the
solvent.
• The increase in disorder is independent of the identity of the species used
to bring it about the change.
• It is however dependent on the number of solute particles present and not
their chemical identity. These properties are called colligative properties.
• A 0.01 mol kg−1 aqueous solution of any nonelectrolyte is expected to have
the same boiling point, freezing point, and osmotic pressure.
• Molality (m) is defined as the number of moles of solute per kilogram of
solvent 6
 Activity
• Molality = moles of solute/1 kg of solvent
• The unit is m.

Calculate the molality of the following solution:

• 20.0 g of Br2 in 40.0 g of CH2Cl2

7
 Colligative Properties of
solution
• An ideal solute has no effect on the enthalpy (H) of a solution. That is ∆Hmix = 0
• An ideal solute impacts the entropy (S) by introducing a degree of disorder that is
not present in the pure solvent.
• ΔS > 0 when two components mix to give an ideal solution.
• A solute has the ability to modify the physical properties of the solution.

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 Colligative Properties of
solution
The colligative properties of solutions are:
• vapor pressure depression
• boiling point elevation
• freezing point depression
• osmotic pressure

9
Colligative Properties of
solution

10
 Vapour Pressure Depression
• When a nonvolatile solute is added to a solvent, the vapor pressure of the solvent
above the solution is lower than the vapor pressure above the pure solvent.
• This occurs because the presence of the solute molecules at the surface of the
solution reduces the surface area available for the solvent to escape the solution
into the gas phase.
• So, the reduction in vapor pressure of the solvent is proportional to the number of
solute particles (molecules or ions) in solution.

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Vapour pressures Vapour pressures
of pure water of sugar solution

12
 Vapor Pressure Depression
• This relationship is described by Raoult’s law, which states that the vapor pressure
of the solvent (Psolv) is directly proportional to the mole fraction of solvent (χsolv) in
the solution;
Psolv = χ solv Po solv

where Posolv is the vapour pressure of the pure solvent.

• So according to Raoult’s law;
when χsolv = 1, Psolv =
Po solv 13

when χsolv < 1, Psolv <

o
 Vapour Pressure Depression
• Remember that although the chemical nature of the solute does not affect the
vapor pressure depression, the number of solute species does.
• The mole fraction of the solvent must include all the species in solution.
• For sucrose,
χ = nsolv/(nsolv+nsucrose)

• For NaCl,
χ = nsolv/(nsolv+ 2nNaCl).
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 Boiling Point Elevation
• The normal boiling point of any liquid is the point where its vapor pressure reaches 1 atm.
• Because of the vapor pressure depression, when the solvent contains a nonvolatile solute,
the solution will have a vapor pressure less than 1 atm at the normal boiling temperature.
• So, in order to reach a vapor pressure of 1 atm, the solution must be raised to a temperature
higher than the normal boiling point.
• The boiling point elevation is calculated from a form of Raoult’s law except that the amount
of solute particles is expressed as a molality of solute instead of a mole fraction of solvent.

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Normal Melting and Boiling
Normal melting and boiling points
points
The normal melting and boiling points are those when the pressure is 1 atmosphere. These can be
found from the phase diagram by drawing a line across at 1 atmosphere pressure.
 Boiling Point Elevation
• Molality is used for the concentration of solute instead of molarity because it is not affected by changes in temperature.
• The increase in boiling point of the solution (ΔTsoln) is directly proportional to the concentration (in molality) of the
nonvolatile solute in a solvent;

ΔTsoln = Kb m
• where Kb is the molal boiling point elevation constant of the solvent and msolute is the molal concentration of the solute
species. solute

• The constant Kb is proportional to the heat of vaporization of the solvent, which varies depending on the strength of the
intermolecular interactions between the solvent molecules.
• So, Kb has a specific value depending on the identity of the solvent.
• Δtsoln is added to the normal boiling point of the solvent. 17
 Freezing Point Depression
• The freezing point of a pure liquid is the temperature at which the molecules begin to cluster
to form a crystal lattice.
• Since the freezing point is also the melting point, at this temperature there is a dynamic
equilibrium where the rate of freezing equals the rate of melting.
• While some of the solvent molecules cluster together to form a pure solvent crystal lattice,
the liquid solution becomes more concentrated.
• According to Le Chatelier’s principle, the dynamic equilibrium will tend to shift in the
direction of melting to correct the concentration difference between the pure solid and the
solution.
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 Freezing Point Depression
• So, the rate of freezing proceeds slower than the rate of melting, and in order for the dynamic equilibrium to be
reestablished, the freezing must occur at a lower temperature for the solution than for the pure solvent.
• The freezing point depression of a solution is proportional to the molality of the solute species in the same way
as for the boiling point elevation;

ΔTsoln = Kf m
• where Kf is the molal freezing point depression constant of the solvent, which depends on the strength of the
solute
intermolecular interactions between the solvent molecules and so depends on the identity of the solvent.
• Δtsoln is subtracted from the normal freezing point of the solvent.

20
 Freezing Point Depression
• Freezing point depression is used in many everyday applications.
• For example, salting of roadways takes advantage of this effect to lower the freezing
point of ice in cold weather so that it will form at lower than normal temperatures.
• The maximum depression of the freezing point using NaCl is about 18°C (0°F), so if
the ambient temperature is expected to drop below this limit calcium chloride can be
used instead.
• Since CaCl2 dissolves to give three ions instead of two, it will result in a maximum
freezing point depression of 27°C.
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 Freezing Point Depression
• Another everyday practical application of freezing point depression as well as
boiling point elevation is the use of ethylene glycol, a nonvolatile alcohol, in
automobile cooling systems.
• Ethylene glycol lowers the freezing point of the water-ethylene glycol solution so
that it will not freeze in winter months in most climates.
• It also raises the boiling point of the coolant mixture to prevent engine overheating
in hot weather.

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Boiling point elevation and
freezing point depression

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 Activity
• What is the boiling point and freezing point for a 0.501 m solution of glucose? Kb =
0.51oC/m; Kf = 1.86 oC/m

• Recall: ΔTsoln = Kf m solute

ΔTsoln = Kb m solute

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 Osmotic Pressure
• Osmosis is the process in which a liquid passes through
a semipermeable membrane whose pores are large
enough to permit the passage of solvent molecules, but
are too small for the larger solute molecules to pass
through.
• Normally, in an aqueous solution the transport of solvent
through a semipermeable membrane obeys Le
Chatelier’s principle, flowing from an area of low solute
concentration (high solvent concentration) to an area of
high solute concentration (lower solvent concentration).

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 Osmotic Pressure
• Pressure must be applied to the area of higher
concentration to prevent the flow of water entering.

• Osmotic pressure is the minimum pressure which

needs to be applied to the solution to prevent the
inward flow of water across the semipermeable
membrane.

• It is also defined as the measure of the tendency of

a solution to take in water by osmosis.
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 Osmotic Pressure
• The osmotic pressure (Π) of a solution is calculated as;
Π = MRT
• where M is the molar concentration of the dissolved species, R is the ideal gas
constant, and T is the temperature in Kelvin.
• Theoretically, since all the colligative properties are related to the concentration of
solute in solution, the molar mass of the solute can be obtained by measuring one
of the colligative properties of the solution, the mass of the solute, and the mass or
volume of the solvent.
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 Osmotic Pressure
• But, measurements of vapor pressure depression and boiling point elevation are
not very sensitive to changes in the solute concentration and are not usually used
for molar mass determinations.
• The colligative properties more commonly used are measurements of freezing
point depression for solvents with a large Kf and osmotic pressure.
• Osmotic pressure is the most sensitive to changes in solution concentration and
can be used to determine the molar mass of molecules with a low water solubility
such as large biomolecules.
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 Activity

• URL: joinmyquiz.com
• Game code: Lecturer will provide
• Click start.

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 Phase Diagram
• Substances can also transition from a solid directly to a gas without passing through the liquid state,
called sublimation.
• The transition from a gas to a solid directly without passing through the liquid state is called deposition.
• The formation of a plasma by super heating a gas is known as ionization and the reverse transition
from a plasma back to the classical gas state is known as recombination.
• Superfluids can be formed by super cooling any of the three classical states of matter (e.g., solids,
liquids, or gases) known as coalescence.
• The phase changes of pure substances as a function of temperature and pressure are
commonly presented as a phase diagram.

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 Phase Diagrams
One Component system
• The red curve is the phase boundary between the solid and
liquid phase and the temperature and pressure conditions
where melting and freezing occur.
• The blue curve is the phase boundary between the liquid and
gas phase and the temperatures and pressures where
vaporization and condensation occur.
• The green curve is the phase boundary between the solid
and gas phase and the temperature and pressure conditions
where sublimation and deposition occur.
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 Phase Diagram
• The point where all three boundaries join is known as the
triple point (tp) of the pure substance.
• The temperature and pressure of the triple point are the
conditions where all three classical phases of matter can
coexist simultaneously.
• The phase boundary between the liquid and gas phases
ends at a point called the critical point (cp).
• The temperature at this point is known as the critical
temperature (Tcr) and the pressure at this point is the critical
pressure (Pcr).
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 Phase Diagram
• Above the critical point, the liquid and gas phases become indistinguishable.
• The substance becomes a supercritical fluid with properties of both gas and liquid phases.
• Supercritical fluids are compressible and diffuse rapidly like gases, but with densities similar to liquids.
• Near the critical point, a small change in pressure or temperature results in a large change in the
density of the supercritical fluid.
• In addition, since there is no liquid-gas phase boundary above the critical point, there is no surface
tension.
• The most common supercritical fluid is carbon dioxide, which is used for the decaffeination of coffee
beans and as a replacement for organic solvents in “greener” dry cleaning procedures.
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Phase Diagram
H2 O CO2
 Phase Rule
• F = C - P +2
• Degrees of freedom (f) is the number of external variables that can be changed independently
without disturbing the number of phases in equilibrium e.g. pressure, temperature and
composition
• Components is a chemically independent constituent of a system.
• Number of component (c) is the minimum number of independent species necessary to define
the composition of all the phase present in the system.
• Phase (p) is the state of matter that is uniformed throughout in chemical composition and
physical state.
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 Phase Rule
• For a one-component system (eg: pure water):
 C = 1, therefore phase rule simplifies to F = 3 - P
 When only one phase present, F = 2 (which implies p and T can be varied
independently)
 When two phases are in equilibrium F = 1 (p is not freely variable with a
set T)
 When three phases are in equilibrium F = 0 (invariable) – Triple point
• For two-component systems (binary mixtures):
 C=2, therefore F = 4 – P
 If p is kept constant, then F’ = 3 – P (F’ is the number of degrees of
36
freedom remaining)
 Raoult’s law
• The partial vapour pressure of a substance in
a liquid mixture is proportional to its mole
fraction in the mixture and its vapour pressure
when pure:
pJ = xJ pJ*
pJ* is the vapour pressure of the pure substance.

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 Raoult’s law
• The molecular origin of Raoult’s law is the effect of the solute on the entropy of the solution.
• The molecules have a certain disorder and a corresponding entropy in a pure solvent. When a
solute is present, the solution has a greater disorder than the pure solvent.
• The entropy of the solution is therefore higher than that of the pure solvent.
• The solution has a lower tendency to acquire an even higher entropy by the solvent vaporizing.
• The vapour pressure of the solvent in the solution is lower than that of the pure solvent, since
the vapour pressure then represents the tendency of the system and its surroundings to reach a
higher entropy.

38
 Ideal Solutions
• An ideal solution is a hypothetical solution of a solute B in a solvent A that obeys
Raoult’s law throughout the composition range from pure A to pure B.
• The law is most reliable when the components of a mixture have similar molecular
shapes and are held together in the liquid by similar types and strengths of
intermolecular forces.
• A mixture of benzene and toluene is a good approximation to an ideal solution.
• The partial vapour pressure of each component satisfies Raoult’s law reasonably
well throughout the composition range from pure benzene to pure toluene.
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 Limitation of Raoult’s law

Raoult's Law only works for:

• Ideal solutions – a solution which obeys Raoult's Law.
 Only very dilute solution obeys this laws.
 The forces of attraction between solvent and solute are exactly the same as between the
original solvent molecules
 Ideal Solutions
• Mixture are not perfectly ideal and all real mixtures show deviations from Raoult’s
law.
• However, the deviations are small for the component of the mixture that is in large
excess (the solvent) and become smaller as the concentration of solute decreases.
• In a dilute solution, each solute molecule is surrounded by nearly pure solvent.
• The environment is quite unlike that in the pure solute and it is very unlikely that its
vapour pressure will be related in a simple manner to that of the pure solute, except
when solute and solvent are very similar (such as benzene and methylbenzene).
41
 Ideal Solutions
• However, it is found experimentally that in dilute solutions the vapour pressure of the
solute is in fact proportional to its mole fraction, just as for the solvent.
• Unlike the solvent, though, the constant of proportionality is not in general the vapour
pressure of the pure solute.
• Raoult’s law provides a good description of the vapour pressure of the solvent in a
very dilute solution, when the solvent A is almost pure.
• However, we cannot in general expect it to be a good description of the vapour
pressure of the solute B because a solute in dilute solution is very far from being pure.
42
 Examples of ideal mixtures

• There is actually no such thing as an ideal mixture! However, some liquid mixtures
get fairly close to being ideal. These are mixtures of two very closely similar
substances.
• Commonly quoted examples include:
 hexane and heptane
 benzene and methylbenzene
 propan-1-ol and propan-2-ol

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 Vapour Pressure / Composition
Diagrams
• Suppose you have an ideal mixture of two liquids A and B. Each of A and B is making its own
contribution to the overall vapour pressure of the mixture.
Ptot = PA + PB

• Suppose you double the mole fraction of A in the mixture (keeping the temperature constant).
According to Raoult's Law, you will double its partial vapour pressure. If you triple the mole fraction,
its partial vapour pressure will triple - and so on.
• In other words, the partial vapour pressure of A at a particular temperature is proportional to its mole
fraction. If you plot a graph of the partial vapour pressure of A against its mole fraction, you will get a
straight line.
Vapour Pressure / Composition
Diagrams
Now we'll do the same thing for B - except that we will plot it on the same set of axes. The mole
fraction of B falls as A increases so the line will slope down rather than up. As the mole fraction of B
falls, its vapour pressure will fall at the same rate.
Notice that the vapour pressure
of pure B is higher than that of
pure A.

That means that molecules

must break away more easily
from the surface of B than of A.

B is the more volatile liquid.

To get the total vapour pressure

of the mixture, you need to add
the values for A and B together
at each composition.

The net effect of that is to give

you a straight line as shown in
the next diagram.
 Boiling point / composition
diagrams
• If a liquid has a high vapour pressure at a particular temperature, it means that its
molecules are escaping easily from the surface.
• If, at the same temperature, a second liquid has a low vapour pressure, it means
that its molecules aren't escaping so easily.
• What does that imply about the boiling points of the two liquids?
There are two ways of looking at this:
EITHER

• If the molecules are escaping easily from the surface, it must mean that the
intermolecular forces are relatively weak. That means that you won't have to
supply so much heat to break them completely and boil the liquid.

• The liquid with the higher vapour pressure at a particular temperature is the one
with the lower boiling point.
49
OR

• Liquids boil when their vapour pressure becomes equal to the external pressure. If
a liquid has a high vapour pressure at some temperature, you won't have to
increase the temperature very much until the vapour pressure reaches the
external pressure. On the other hand if the vapour pressure is low, you will have to
heat it up a lot more to reach the external pressure.

• The liquid with the higher vapour pressure at a particular temperature is the one
with the lower boiling point.
50
Constructing a boiling point /
Composition diagram
Constructing a boiling point /
Composition diagram
To make this diagram really useful (and
finally get to the phase diagram we've been
heading towards), we are going to add
another line. This second line will show the
composition of the vapour over the top of any
particular boiling liquid.

If you boil a liquid mixture, you would expect

to find that the more volatile substance
escapes to form a vapour more easily than
the less volatile one.

That means that in the case we've been

talking about, you would expect to find a
higher proportion of B (the more volatile
component) in the vapour than in the liquid.
You can discover this composition by
condensing the vapour and analysing it. That
would give you a point on the diagram.
 Using the phase diagram
• If you boil a liquid mixture C1, it will boil at a temperature
T1 and the vapour over the top of the boiling liquid
will have the composition C2.

• All you have to do is to use the liquid composition

curve to find the boiling point of the liquid, and then
look at what the vapour composition would be at that
temperature.
• Notice again that the vapour is much richer in the
more volatile component B than the original liquid
mixture was.
• Suppose that you collected and condensed the
vapour over the top of the boiling liquid and reboiled
it.

• You would now be boiling a new liquid which had a

composition C2.

• That would boil at a new temperature T2, and the

vapour over the top of it would have a composition
C3. You can see that we now have a vapour which is
getting quite close to being pure B. If you keep on
doing this (condensing the vapour, and then reboiling
the liquid produced) you will eventually get pure B.
 Fractional
distillation of ideal
mixtures of liquids
 Fractional
distillation of ideal
mixtures of liquids
azeotro • Phase diagram may look different for a
pe number of important cases.
• Maximum/minimum in boiling point curve
• In the case of a maximum, there is
favourable interactions between the
molecules which reduce the vapour
pressure of the mixture (less volatile)
below the ideal value. Eg:
chloroform/water
• In the case of a minimum, there is
unfavourable interactions which result
in a more volatile mixture. Eg:
dioxane/water

57
 Problem

An ideal mixture of two liquids A and B contained 1 mole of A and 4

moles of B. The vapour pressure of pure A at the temperature of the
mixture was 10 kPa, and that of pure B was 12.5 kPa.

(i) Calculate the partial vapour pressure of A in the mixture.

(ii) Calculate the partial vapour pressure of B in the mixture.
(iii) Calculate the total vapour pressure of the liquid.

58
 Definitions

• Colligative properties of a solution depend upon the concentration of solute molecules or

ions, but not upon the identity of the solute.
• Phase diagram is a graphical representation of the phase changes of pure substances as a
function of temperature and pressure
• Plasma an ionized gas occurring typically at low pressures or at very high temperatures.
• Supercritical fluid is a substance at a temperature and pressure above its critical point
where distinct liquid and gas phases do not exist.
• Superfluid is a state of matter which behaves like a fluid with zero viscosity
59
 Definitions
• Triple point (tp) is the temperature and pressure where all three classical phases, solid,
liquid, and gas, can coexist simultaneously
• Molarity (M) is defined as the number of moles of solute per liter of solution.
• Molality (m) is defined as the number of moles of solute per kilogram of solvent
• Raoult’s law is the vapor pressure of the solvent is directly proportional to the mole
fraction of solvent in the solution
• Azeotrope is a mixture of two liquids that has a constant boiling point and
composition throughout.
60
 Immiscible Mixtures
• Mixtures in which the components do not dissolve in each
other is referred to as immiscible.
• When liquids are immiscible, they cannot be separated by
distillation, as previously discussed.
• Separation of immiscible liquids can be accomplished by:
• Solvent-solvent extraction
• Solid phase extraction

61
 Immiscible Mixtures
• The distribution of a solute between two phases
is an equilibrium condition described by
partition theory.

• This is based on exactly how the analyte move

from the water into an organic layer.

62
 Partition
Coefficient
• At a certain temperature, the
ratio of the concentrations of a
solute in each solvent is always
constant.

KD = Corg / Caq

o KD = Partition or distribution
coefficient
o Corg = Concentration in organic
phase
o Caq = Concentration in the
aqueous phase 63
 Problem
In extracting Compound X from a solution, the organic phase was isolated
and allowed to evaporate, leaving behind 1.235 g of the solute (compound
X) with a molar mass of 117.3 g/mol which was then dissolved in 10.00 mL
of water. After extracting with 5.00 mL of toluene, 0.889 g of the solute is
recovered in the organic phase. What is the partition coefficient of this
mixture?
Recall, KD = Corg / Caq

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