PHASE EQUILIBRIUM

Introduction
• Mixtures undergo physical changes when they are heated or cooled
and when their compositions are changed.

• Phase diagrams are of considerable commercial and industrial

significance, particularly for semiconductors, ceramics, steels, and
alloys.

Phases, components, and degrees of freedom

All phase diagrams can be discussed in terms of a
relationship, the phase rule, derived by Gibbs.

Relationship between degree of freedom, no of component and phase

F= variance/degree of freedom
F=C-P+2 C= no of component
P= no of phase
 Phase diagram
Phase diagrams display properties of substances, and
combinations of substances, in terms of their
physical state (solid, liquid or gas) under various conditions
(temperature, pressure, and composition).

They give insight to significant differences among individual

substances and assist in understanding
transformations brought by changing conditions
 Phase diagram

Melting point
Solidliquid

Sublimation Boiling
point T
Point
Solid  gas Liquid gas

Normal Normal
melting boiling
point point
 definition
• Phase:
defined as a homogeneous part of the
heterogeneous system
Examples:
Ice : 1 single phase
Ice and water : 2-phase system
Alloy of 2 metals: 2-phase (if immiscible,
but 1-phase system if miscible)
 definition
• Component:
Is the minimum of different substances
required to describe the composition of all
phases in the system.
Example:
Air (O2, N2, CO2 ) – many component
Ice, water – 1 component
Water, CCl4 – 2 component
 Critical point
-the liquid-vapour equilibrium curve has a top limit, labelled
as C in the phase diagram.

This is known as the critical point. The temperature and

pressure corresponding to this are known as the critical
temperature and critical pressure.

If you increase the pressure on a gas (vapour) at a

temperature lower than the critical temperature, you will
eventually cross the liquid-vapour equilibrium line and the
vapour will condense to give a liquid-called as supercritical
fluid.

Above the critical temperature, it is impossible to condense a

gas into a liquid just by increasing the pressure. All you get is
a highly compressed gas. The particles have too much
energy for the intermolecular attractions to hold them
together as a liquid.
The liquid becomes less dense until, at the critical point, the densities of
liquid and vapour become equal, eliminating the boundary between the two
phases.
 Triple point
• Is a point where all phases (solid, liquid and gas)
are present in equilibrium.
• Triple point of water: 0.01oC, 0.006 atm
• Triple point of CO2 : -56.4oC, 5.11 atm.

sublimation:
Solid changes directly to vapor without passing
through the liquid phase. Solid can only sublime
at a temperature below the triple point.
 Degree of freedom
F= variance/degree of freedom
F=C - P+2 C= no of component
P= no of phase
• Is the number of intensive variables (temperature and pressure) that
can be independently varied w/o changing the phase of the system.
• P+F=C+2
P= no of phase
C= no of component

For one component system: C=1 • For 1 component, two phases:

P+F = 1 +2 F=3-2 = 1 (univariant system)
F=3-P
For 1 component ,three phases system:
For one phase, 1 component system: F=3-3 = 0 (invariant system)
F= 3-p
F=3-1= 2 ( bivariant system)
 Normal melting and boiling 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. .                                                                                               
            
 The three areas
suppose you have a pure substance at three different sets of conditions of
temperature and pressure corresponding to 1, 2 and 3 in the next diagram

                                                                                          

1 : solid because it falls into that

area of the phase diagram.

2: it would be a liquid;

3: it would be a vapour (a gas).

Moving from solid to liquid by changing the temperature:
Suppose you had a solid and increased the temperature while keeping
the pressure constant - as shown in the next diagram. As the
temperature increases to the point where it crosses the line, the solid will
turn to liquid.                                                                                                                                       
If you repeated this at a higher fixed pressure, the melting temperature
would be higher because the line between the solid and liquid areas
slopes slightly
forward                                                                                                         
Line separating the solid and liquid areas of the diagram:
shows the effect of pressure on melting point.

Anywhere on this line, there is an equilibrium between solid and liquid.

apply Le Chatelier's Principle to this equilibrium:

If you increase the pressure, the equilibrium will move in such a way as to counter
the change.

       

                                                                                         

If the substances is converted from liquid to solid, the pressure would tend to
decrease again because the solid takes up slightly less space for most substances -
meaning that increasing the pressure on the equilibrium mixture of solid and liquid at
its original melting point will convert the mixture back into the solid again. In other
words, it will no longer melt at this temperature.

-therefore; to make it melt at this higher pressure, you will have to increase the
temperature a bit. Raising the pressure raises the melting point of most solids.
That's why the melting point line slopes forward for most substances.
 Moving from solid to liquid by changing the pressure:
- what happens if you decrease the pressure on a solid at constant
temperature.

If the conditions of
temperature and pressure
fell exactly on that line,
there would be solid and
vapour in equilibrium with
each other - the solid
would be subliming.
 Moving from solid to vapour:
The diagram shows the effect of increasing the temperature of
a solid at a (probably very low) constant pressure. The
pressure obviously has to be low enough that a liquid can't
form - in other words, it has to happen below the point labelled
as T.                                                                                                 
Moving from liquid to vapour:
In the same sort of way, you can do this either by changing the
temperature or the
pressure.                                                                                                        
Increase temperature/dec
                     
pressure: The liquid will change to
a vapour - it boils - when it
crosses the boundary line
between the two areas.

Anywhere along this line,

there will be an equilibrium
between the liquid and the
vapour.
As the pressure increases, so
the boiling point increases.
 One component system
• Phase diagram of water
The solid-liquid equilibrium line (the
melting point line) slopes
backwards rather than forwards.

triple point for water occurs at a very

low pressure. (0.01oC, 0.006 atm).
critical temperature is 374°C.

Normal boiling point: 100oC, 1 atm.

Increase pressure above 1 atm -
raise boiling point and lower the
melting point
One component system
phase diagram of CO2 Slope of the curve between solid and
liquid is +ve.

Entire liquid phase lies above

atmospheric pressure: impossible for
solid carbon dioxide to melt at 1 atm.

meaning that at 1 atmosphere

pressure, carbon dioxide will sublime
at a temperature of -78°C.

This is the reason that solid carbon

dioxide is often known as "dry ice".
You can't get liquid carbon dioxide
under normal conditions - only the
solid or the vapour.

triple point: 5.2 atm, -57oC

 Examples:
• The boiling point and freezing point of
sulfur dioxide are -10oC and -72.7oC at 1
atm. The triple point is -75.5 oC and 1.65 x
10-3 atm. Its critical point is at 157oC and
78atm. On the basis of this information,
draw a phase diagram of SO2.
 vapor pressure

vapour


liquid

Liquid  vapor
 when the equilibrium between liquid and vapor is reach,
the number of molecules per unit volume in the vapor
does not change
 at equilibrium the vapour pressure is the pressure
exerted by the vapor above its liquid/solid or
 Pressure of the vapour resulting from evaporation of a
liquid/solid in a closed container
 Lower boiling point, higher vapour pressure
 Vapor pressure in mixture of liquids : benzene + toluene

Boiling point toluene = 110.6oC , benzene = 80.1oC

more benzene molecules in vapor phase compared to toluene
 Two-component solution/lquid
Pure liquid:
One type of molecular forces: A…A or B…B

Mixture of liquid A and B

3 types of molecular forces: A…A, B…B and A…B
The ideal solution is form when all the intermolecular forces are of the same
strength: attractions between A..A = A…B = B…B →ideal solution.
However if the strength between A…B is different than A…A or B…B, the
solution become non-ideal.

Pure liquid Mixture of liquid

Liquid A Liquid B Mixtures of

Liquid A + liquid B
 Examples of ideal mixtures

There is actually no ideal mixture of liquid. However,

some liquid mixtures get fairly close to being ideal.
These are mixtures of two very closely similar
substances.

examples include:
hexane and heptane
benzene and methylbenzene
propan-1-ol and propan-2-ol
RAOULT'S LAW AND IDEAL MIXTURES OF LIQUIDS

Raoult's Law
 how it applies to mixtures of two volatile liquids
 cases where the two liquids are entirely miscible in all proportions to
give a single liquid

Ideal mixtures
An ideal mixture is one which obeys Raoult's Law
 what is the characteristics of an ideal mixture

Characteristic of Ideal mixtures of soution

• Obeys the Roult’s law
• Solution with similar intermolecular forces
• There wont be any heat either evolved or absorbed during the
mixing of the two solution/liquid
• Therefore, ΔH = zero during the mixing
 Raoult's Law
The partial vapour pressure of a component in a mixture is
equal to the vapour pressure of the pure component at that
temperature multiplied by its mole fraction in the mixture.

Raoult's Law only works for ideal mixtures.

for a mixture of liquids A and B;                                    

PA and PB : partial vapour pressures of the components A and B.

In any mixture of gases, each gas exerts its own pressure. This is
called its partial pressure and is independent of the other gases
present.
 The total vapour pressure of the mixture is equal to the sum of the
individual partial pressures.

The Po values are the vapour pressures of A and B own as pure liquids.
xA and xB are the mole fractions of A and B.

mole fraction :
                                                                    
 EXAMPLE

At 25 oC the vapour pressure of pure benzene and toluene are 93.4 mmHg and
26.9 mmHg. If the mixture contains 60.0g of benzene and 40.0 g of toluene,
calculate the vapour pressure of this solution

PT = P A + P B Calculate the number of moles for benzene and

@ toluene:
Ptotal = XA PoA + XB PoB n of benzene : = 60/78 = 0.77 mole
n of toluene : = 40/92 = 0.43 mole
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
 Vapour pressure / composition diagrams (ideal solution)

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 - as we've seen above.
Let's focus on one of these liquids - A, for example.

According to Raoult’s law, 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.
for B - if we will plot B on the same set of axes; the mole fraction of B falls as A increases so
the line will slope. As the mole fraction of B falls, its vapour pressure will fall at the same
rate.                                                                                                                                                                            
*Notice that the vapor
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.

Total vapour pressure

of the mixture:
Add the values for A and
B together at each
composition
                                                      
             
 Boliling point / composition diagrams
The relationship between boiling point and vapour pressure
If a liquid has a high vapour pressure at a particular temperature, it
means that its molecules are escaping easily from the surface.
If, 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?
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.
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. 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.
 Constructing a boiling point / composition diagram
Liquid with the higher vapour pressure at a particular temperature is the one with
the lower boiling point.
Therefore, for two liquids at the same temperature, the one with the higher
vapour pressure is the one with the lower boiling point.

Boiling A and B mixtures:

The more volatile substances
escapes to form a vapour more
easily than the less volatile one.
Higher propotion of B in the
vapour than in liquid.
Vapour over the top of the
boiling liquid has composition
which is much richer in B – the
more volatile component.

Composition diagram
If you boil a liquid mixture C1, you will get a vapour with composition C2,
which you can condense to give a liquid of that same composition (the
pale blue lines).
If you reboil that liquid C2, it will give a vapour with composition C3.
Again you can condense that to give a liquid of the same new
composition (the red lines).
Reboiling the liquid C3 will give a vapour still richer in the more volatile
component B (the green lines). You can see that if you were to do this
once or twice more, you would be able to collect a liquid which was
virtually pure B.
The apparatus for the fractional distillation
 Mixture of liquids

Ideal solution/mixture Non-ideal

(Obey Roults law) solution/mixture

+ve deviation
(actual pressure
higher than calculated -ve deviation
by Roults law) (actual pressure lower
than calculated by
Roults law)
 1: Positive deviations from Raoult's Law
In mixtures showing a positive deviation from Raoult's Law, the vapour
pressure of the mixture is always higher than you would expect from an
ideal mixture

The deviation can be small - in which case, the straight line in the
last graph turns into a slight curve
But
some liquid mixtures have very large positive deviations from
Raoult's Law, and in these cases, the curve becomes very
distorted.                                                                                                    
                
 Explaining the deviations

The fact that the vapour pressure is higher than ideal in these mixtures
means that molecules are breaking away more easily than they do in the
pure liquids.

That is because the intermolecular forces between molecules of A and B

are less than they are in the pure liquids.
You can see this when you mix the liquids. Less heat is evolved when the
new attractions are set up than was absorbed to break the original ones.
Heat will therefore be absorbed when the liquids mix. The enthalpy change
of mixing is endothermic.

The classic example of a mixture of this kind is ethanol and water. This
produces a highly distorted curve with a maximum vapour pressure for a
mixture containing 95.6% of ethanol by mass.
 Boiling point-positive deviation

Azeotropic
mixture

Azeotropic mixture: mixture with a constant boiling point where the

composition of the vapour is the same as the composition of the liquid.
SAMPAI SINI 10 june 2021
• reboiling the azeotropic liquid:
- vapour produce the same composition of 95.6 % ethanol
- Condensing the vapour will produce the same particular mixture of
ethanol and water boils as if it is a pure liquid.
- What left in the distillation flask is water (residue), as most ethanol is
given off from the boiling liquid and collected as distillate.

 Some other examples:

- Water + hexanol
- Ethanol + chloroform
- Ethanol + toluene
- Ethanol + benzene
Ethanol 95%
(distillate)
Water
(residue)
 Examples:
• Ethanol (boiling point=78.5oC) and water (boiling point=100oC) form
an azeotropic mixture with a composition of 95% water by mass and
a boiling point of 78oC.
A) sketch a vapour pressure-composition graph for the water/ethanol
system
B) sketch a boiling point-composition graph for the water/ethanol
system, and explain what happens when a mixture containing 50%
ethanol by mass is distillated fractionally.
C) suggest how pure ethanol can be obtained from the azeotropic
mixture.
 2: Negative deviation from Raoult’s law
Negative deviations from Raoult's Law

we can have mixtures with vapour pressures which are less than
would be expected by Raoult's Law. In some cases, the deviations
are small, but in others they are much greater giving a minimum
value for vapour pressure lower than that of either pure component.
• Explanation negative deviation:
• Due to the stronger molecular interaction between A ….B
molecules compared to pure liquid A…A or B…B
• Therefore, the molecules have lower tendency to vaporise in
the mixture compared to in the pure liquid, causing the
vapour pressure to be lower than expected
• Example: mixture of ether (b.p=35.0oC) and
trichloropmethane (b.p = 61.2oC).

CCl3 – H… CCl - H
3
C2H5 –O - C2H5…. C2H5 -O - C2H5

Van der waals forces

 However, when the liquid mixed, a stronger intermolecular
forces is formed between dichloromethane and ether,
which is called hydrogen bonding.

Cl3 – C – H+ -
O – (C2H5 )2
Hydrogen bonding
Due to th estrong intermolecular interaction, the vapour pressure-composition
graph shows a minimum in the vapour pressure/composition curve.
 Boiling point-negative deviation
-the boiling point-composition graph shows a maximum .
-eg : HNO3 and water; HCl and water

Azeotropic
mixture
 example

Water (boiling point =100oC) and nitric acid (boiling

point=86oC) forms an azeotrope (boiling point=120.5oC)
containing 68% nitric acid by mass.

a)Sketch (i) the vapour pressure-composition and (ii)

boiling point composition graph for the system.
b)Explain what happen when a mixture containing 50%
nitric acid is subjected to fractional distillation.
SOLID-LIQUID PHASE DIAGRAMS: TIN AND LEAD
the relationship between the cooling curves for liquid
mixtures of tin and lead, and the resulting phase diagram.
introduction to the idea of a eutectic mixture.

Cooling curves for pure substances

Suppose you have some pure molten lead and allow it to cool down until it
has all solidified, plotting the temperature of the lead against time:
 Explanation:
Throughout the whole experiment, heat is being lost to
the surroundings - and yet the temperature doesn't fall
at all while the lead is freezing. This is because the
freezing process liberates heat at exactly the same rate
that it is being lost to the surroundings.

Energy is released when new bonds form - in this case,

the strong metallic bonds in the solid lead.

If you repeated this process for pure liquid tin, the shape
of the graph would be exactly the same, except that the
freezing point would now be at 232°C.
 Cooling curves for tin-lead mixtures
If you add some tin to the lead, the shape of the cooling curve
changes. The graph shows what happens if you cool a liquid
mixture containing about 67% lead and 33% tin by
mass.                                                                                                         
 Cooling curve: lead and tin:
Notice that nothing happens at all at the normal freezing
point of the lead.
Adding the tin to it lowers its freezing point.
Freezing starts for this mixture at about 250°C -some solid
lead formed - but no tin. At that point the rate of cooling
slows down - the curve gets less steep.
However, the graph doesn't go horizontal yet. Although
energy is being given off as the lead turns to a solid, there
isn't anything similar happening to the tin. That means that
there isn't enough energy released to keep the temperature
constant.
The temperature does stop falling at 183°C. Now both tin
and lead are freezing. Once everything has solidified, the
temperature continues to fall.
Eutectic diagram
Start with mixture of
67%Pb & 33%Sn Lead start to freeze when the
temperature falls to here (250oC)

The temperature &

Solid x composition of liquid
lead move along the line
as far as the eutectic
point
Y
Eutectic
temperature

When the first lead freezes, the composition of the remaining liquid changed-
become richer in tin. Therefore the freezing point of lead lowers-liquid get richer
and richer in tin until the eutectic point is reached.
Once the eutectic point is reached-the system move into the region of a mixture
of solid lead and solid tin-all the remaining liquid freezes.
Point x: solid lead + liquid with Y composition.
 Temperature C o
Example
Eutectic diagram
Frezing point of
pure B, C Higher freezing point of pure B lower freezing point of pure A
E
A (l) + B (l) Frezing point of
pure A,

B(s)+(A+ B) D A(s) + (A + B) (l)

(l)
Eutectic
A (s) + B (s) temperature

70% A
100% B 100% A
From C to D:
B will freeze first. The freezing temperature is getting lower due to the presence of the impurities (A). A will freeze together with B when the
eutectic point (D) is reach.
From D to E:
A is started to freeze at D, then more A is freezing, but B is still in the liquid form.
The freezing temperature of A is getting higher due to the existence of B (B has
higher melting point than A).
 Example:
P
Z
x Q
Y

100 %Ag 100 %Cu

What does the temperature at point x represent?

(melting point of pure silver)

Consider a molten mixture, containing equal masses of silver and copper was allowed to cool
down from a temperature at P. At what temperature do the first crystal of solid appear?
What is the percentage of silver in this first crystal? (at Q) (0%)
(melts at a single defined temperature at Y) (and produce a liquid melt containing copper and silver)

Explain what is meant by the term eutectic mixture at Y

(liquid has same composition as the solid)
Colligative Properties of Solutions:
• Colligative properties are properties of solutions that
depend solely on the number of particles dissolved in the
solution.

–Colligative properties do not depend on the kinds of

particles dissolved.
• Colligative properties are a physical property of solutions.

• four common types of colligative properties:

1.Vapor pressure lowering
2.Boiling point elevation
3. Freezing point depression
4.Osmotic pressure
 Lowering of Vapor Pressure and Raoult’s Law
• Addition of a nonvolatile solute to a solution lowers the vapor pressure
of the solution.
– The effect is simply due to fewer solvent molecules at the solution’s
surface.
– The solute molecules occupy some of the spaces that would normally
be occupied by solvent.

 Adding a nonvolatile solute lowers the

vapor pressure of the solvent since a
smaller proportion of the molecules at
the surface of the solution are solvent
molecules, fewer solvent molecules
can escape from the solution
compared to the pure solvent.
Boiling Point Elevation
• Addition of a nonvolatile solute to a solution raises the
boiling point of the solution above that of the pure solvent.

– This effect is due to the solution’s vapor pressure is

lowered as described by Raoult’s law.

Boiling point elevation relationship is:

ΔTb = Kbm
ΔTb = the amount by which the boiling point is raised
m = molality (moles solute particles per kg of solution)
Kb = molal boiling-point elevation constant
(solvent dependent)
Boiling Point of solution = normal boiling point of solvent + ΔT
b
 
Freezing Point Depression
Addition of a nonvolatile solute to a solution lowers the
freezing point of the solution relative to the pure solvent.
ΔTf = -Kfm
ΔTf = the amount by which the freezing point is lowered
m = molality (moles solute particles per kg of solution)
Kf = molal freezing-point depression constant (solvent dependent)
Freezing Point of solution = normal freezing point of solvent + ΔT
f
The freezing-point depression is proportional to the
concentration of solute particles expressed as moles of solute
per kilogram of solvent.

Notice the similarity of the two relationships for freezing

point depression and boiling point elevation.
ΔTf = Kfm vs ΔTb = Kbm

• Fundamentally, freezing point depression and boiling

point elevation are the same phenomenon.
Colligative Properties and Dissociation of Electrolytes
• Electrolytes have larger effects on boiling point elevation and
freezing point depression than nonelectrolytes.
–This is because the number of particles released in solution is
greater for electrolytes
• One mole of NaCl dissolves in water to produce two moles of
aqueous ions:
–1 mole of Na+ + 1 mole of Cl- ions

The van’t Hoff factor, symbol i, is used to introduce this

effect into the calculations.
• i is a measure of the extent of ionization or dissociation of
the electrolyte in the solution.

i= ΔTf (actual)
ΔTf (if nonelectrolyte)
 Examples:
i has an ideal value of 2 for 1:1 electrolytes like NaCl, KI, LiBr, etc.

NaCl → Na+ + Cl- : 2 ions/formula unit

i has an ideal value of 3 for 2:1 electrolytes like K2SO4, CaCl2, SrI2, etc.

CaCl2 → Ca 2+ + Cl- : 3 ions/formula unit

Some Boiling-Point Elevation and Freezing-Point Depression Constants

normal boiling normal freezing

solvent Kb (oCm-1) Kf (oCm-1)
point (oC) point (oC)

benzene 80.2 2.53 5.5 5.12

water 100.0 0.512 0.000 1.855

acetic acid
118.5 3.07 16.6 3.90
(ethanoic acid)

camphor 208.3 5.95 178.4 40.0

naphthalene 218.0 5.65 80.2 6.9

 Example: Calculating Boiling and Freezing Point of a Nonelectrolyte Solution
For a 0.262m solution of sucrose in water, calculate the freezing point and the boiling
point of the solution.

1. Calculate the freezing point depression:
ΔTf = -Kfm
Kf = 1.855 (from table above)
m = 0.262m
ΔTf = -1.855 x 0.262 = -0.486oC
Calculate the freezing point of the solution:
Tf (solution) = normal freezing point +
TΔT
f (solution)
f = 0.000 - 0.486
                  = -0.486oC
1. Calculate the boiling point elevation:
ΔTb = Kbm
Kb = 0.512 (from table above)
m = 0.262m
ΔTb = 0.512 x 0.262 = 0.134oC
Calculate the boiling point of the solution:
Tb (solution) = normal boiling point + ΔTb
Tb (solution) = 100.00 + 0.134
                  = 100.134oC
Example: Calculating Boiling and Freezing Point of an Electrolyte Solution

Calculate the freezing point and boiling point for a 0.15m aqueous solution of sodium
chloride.

1. Calculate the freezing point depression: 1. Calculate the boiling point elevation:
ΔTf = -Kfm ΔTb = Kbm
Kf = 1.855 (from table above) Kb = 0.512 (from table above)
Since: NaCl → Na+(aq) + Cl-(aq): Since: NaCl → Na+(aq) + Cl-(aq):
m(Na+) = 0.15m m(Na+) = 0.15m
m(Cl-) = 0.15m m(Cl-) = 0.15m
m(NaCl(aq)) = 0.15 + 0.15 = 0.30m m(NaCl(aq)) = 0.15 + 0.15 = 0.30m
ΔTf = -1.855 x 0.30 = -0.557oC ΔTb = 0.512 x 0.30 = 0.154oC
Calculate the freezing point of the solution: Calculate the boiling point of the solution:
Tf (solution) = normal freezing point + ΔTf Tb (solution) = normal boiling point + ΔTb
Tf (solution) = 0.000 - 0.557 Tb (solution) = 100.00 + 0.154
                  = -0.557oC                   = 100.154oC
Example: Calculating Molecular Mass (Formula Weight) of Solute
1.15g of an unknown, nonvolatile compound raises the boiling point of 75.0g benzene
(C6H6) by 0.275oC.
Calculate the molecular mass (formula weight) of the unknown compound.
1.Calculate the molality of solute particles:
m = ΔTb ÷ Kb
ΔTb = 0.275oC
Kb = 2.53oCm-1 (from table above)
m = 0.275 ÷ 2.53 = 0.109m
2.Calculate the moles of solute present:
molality = moles solute ÷ kg solvent
n(solute) = m x kg solvent = 0.109 x 75.0 x 10-3 = 8.175 x 10-3 mol
Calculate the molecular mass (formula weight) of the solute:
n(solute) = mass(solute) ÷ MM(solute)
MM(solute) = mass(solute) ÷ n(solute) = 1.15 ÷ 8.175 x 10-3 = 141 g/mol
Osmotic Pressure
• Osmosis is the net flow of a solvent molecules between
two solutions separated by a semipermeable membrane.
– The solvent passes through from the lower concentration
solution into the higher concentration solution.

• Examples of semipermeable
membranes include:
1.cellophane and saran wrap
2.skin
3.cell membranes

Van Hoff Eq : Π = MRT

•In dilute solutions, osmotic pressure (Π) is directly proportional to the molarity of
•the solution and its temperature in Kelvin.

van't Hoff Equation:

Π = MRT
    Π = osmotic pressure
    M = molarity = moles ÷ volume(L)
    R = ideal gas constant
    T = temperature (K)
•Solvent can be removed from a solution using a pressure greater than the osmotic
•pressure. This is known as reverse osmosis.

Example: Osmotic Pressure Calculation for a Nonelectrolyte Solution

Calculate the osmotic pressure exhibited by a 0.10M sucrose solution at 20oC.

Π = MRT
Π = MRT
M = 0.10M
M = 0.10M
R = 0.0821 L atm K-1mol-
1
R = 8.314 J K-1 mol-1
T = 20oC = 20 + 273 =
T = 20oC = 20 + 273 =
293K
293K
Π = 0.10 x 8.314 x 293 =
Π = 0.10 x 0.0821 x 293
243.6 kPa
= 2.4 atm
 Example: Osmotic Pressure Calculation for an Electrolyte Solution
Calculate the osmotic pressure exhibited by a 0.42M KOH solution at 30oC.

Π = MRT
Π = MRT
Since KOH → K+(aq) + OH-(aq)
Since KOH → K+(aq) + OH-(aq)
M(K+(aq)) = 0.42mol/L
M(K+(aq)) = 0.42mol/L
M(OH-(aq)) = 0.42mol/L
M(OH-(aq)) = 0.42mol/L
M(solute) = 0.42 + 0.42 =
M(solute) = 0.42 + 0.42 =
0.84mol/L
0.84mol/L
R = 0.0821 L atm K-1mol-1
R = 8.314 J K-1 mol-1
T = 30oC = 30 + 273 = 303K
T = 30oC = 30 + 273 = 303K
Π = 0.84 x 0.0821 x 303 = 20.9
Π = 0.84 x 8.314 x 303 = 2116 kPa
atm
Example: Calculation of Molecular Mass (Formula Weight) Using Osmotic Pressure
0.500g hemoglobin was dissolved in enough water to make 100.0mL of solution.
At 25oC the osmotic pressure was found to be 1.78 x 10-3 atm.
Calculate the molecular mass (formula weight) of the hemoglobin.
1.Calculate the molarity, M, of the solution:
M = Π ÷ RT
Π = 1.78 x 10-3 atm
R = 0.0821 L atm K-1mol-1
T = 25oC = 25 + 273 = 298K
M = 1.78 x 10-3 ÷ 0.0821 x 298 = 7.28 x 10-5mol/L
2.Calculate the moles, n, of hemoglobin present in solution:
n=MxV
M = 7.28 x 10-5mol/L
V = 100.0mL = 100.0 x 10-3L
n = 7.28 x 10-5mol/L x 100.0 x 10-3 L= 7.28 x 10-6mol
Calculate the molecular mass, MM, of the hemoglobin:
MM = mass ÷ n
mass = 0.500g
n = 7.28 ÷ 10-6mol
MM = 0.500 ÷ 7.28 x 10-6 = 68,681 g/mol