You are on page 1of 41

COLLIGATIVE

PROPERTIES
Unit 9 Chapter 12
Definition:
The properties of a solution that are dependant
only on the number of solute particles in
solution.
Vapor pressure lowering
Boiling point elevation
Freezing point depression
Osmotic pressure
COLLIGATIVE PROPERTIES
The equilibrium vapor pressure of a solvent with a
nonvolatile solute is shown in (a).
The equilibrium vapor pressure of a pure solvent is shown
in (b).
VAPOR PRESSURE
LOWERING
Which equilibrium has a higher vapor
pressure?
VAPOR PRESSURE
LOWERING
The presence of solute particles results in
fewer solvent molecules sitting at the surface
to escape.
VAPOR PRESSURE
LOWERING
According to Raoults Law, the vapor pressure
of a solution with a non-volatile solute is equal
to the vapor pressure of the pure solvent at
that temperature multiplied by its mole fraction.

P
solv
= P
solv

X
solv

VAPOR PRESSURE
LOWERING
The vapor pressure of the solvent is
proportional to the relative number of solvent
molecules at the surface the mole fraction
of the solvent.
When the solute-solvent attractions are stronger than
the original solvent-solvent attractions, the solution
vapor pressure will be lower. This is typically the case
when the solute is nonvolatile.
VAPOR PRESSURE
LOWERING
Definition:
When the vapor pressure of a solvent
containing a solute is compared to the vapor
pressure of the pure solvent, the solutions
vapor pressure is found to be lower.
P
solv
P
solv
= P
VAPOR PRESSURE
LOWERING
Vapor pressure of
the pure solvent
Vapor pressure of
the solvent in
solution
Amount by which
the solvents vapor
pressure changed
Eugenol, C
10
H
12
O
2
, is the chief constituent of oil of clove. It is a
pale yellow liquid that dissolves in ethanol, C
2
H
5
OH; it has a
boiling point of 255C (thus, it has a relatively low vapor
pressure at room temperature). What is the vapor pressure
lowering at 20.0C of ethanol containing 8.56 g of eugenol in
50.0 g of ethanol? The vapor pressure of ethanol at 20.0C is
44.6 mmHg.
VAPOR PRESSURE
LOWERING
P
solv
= P
solv


X
solv

P
solv
P
solv
= P
Solute
Solvent
P
P
solv
= 44.6 mm Hg

P
solv
P
solv
= P
P
solv
P
solv
X
solv
=
P
Eugenol, C
10
H
12
O
2
, is the chief constituent of oil of clove. It is a
pale yellow liquid that dissolves in ethanol, C
2
H
5
OH; it has a
boiling point of 255C (thus, it has a relatively low vapor
pressure at room temperature). What is the vapor pressure
lowering at 20.0C of ethanol containing 8.56 g of eugenol in
50.0 g of ethanol? The vapor pressure of ethanol at 20.0C is
44.6 mmHg.
VAPOR PRESSURE
LOWERING
P
solv
= P
solv


X
solv

P
solv
P
solv
= P
Solute
P
solv
= 44.6 mm Hg

P
solv
P
solv
X
solv
=
P
(44.6) (44.6) X
solv
=
P
Solvent
8.56gEugenol 1mol
164.22g
= 0.0521mol
50.0gEthanol 1mol
46..07g
=1.086mol
Eugenol, C
10
H
12
O
2
, is the chief constituent of oil of clove. It is a
pale yellow liquid that dissolves in ethanol, C
2
H
5
OH; it has a
boiling point of 255C (thus, it has a relatively low vapor
pressure at room temperature). What is the vapor pressure
lowering at 20.0C of ethanol containing 8.56 g of eugenol in
50.0 g of ethanol? The vapor pressure of ethanol at 20.0C is
44.6 mmHg.
VAPOR PRESSURE
LOWERING
P
solv
= P
solv


X
solv

P
solv
P
solv
= P
Solute
P
solv
= 44.6 mm Hg

P
solv
P
solv
X
solv
=
P
(44.6) (44.6) X
solv
=
P
Solvent
X
solv
=
1.086mol
1.086mol + 0.0521mol
X
solv
= 0.954
Eugenol, C
10
H
12
O
2
, is the chief constituent of oil of clove. It is a
pale yellow liquid that dissolves in ethanol, C
2
H
5
OH; it has a
boiling point of 255C (thus, it has a relatively low vapor
pressure at room temperature). What is the vapor pressure
lowering at 20.0C of ethanol containing 8.56 g of eugenol in
50.0 g of ethanol? The vapor pressure of ethanol at 20.0C is
44.6 mmHg.
VAPOR PRESSURE
LOWERING
P
solv
= P
solv


X
solv

P
solv
P
solv
= P
Solute
P
solv
= 44.6 mm Hg

P
solv
P
solv
X
solv
=
P
(44.6) (44.6)(0.954) = P
Solvent
2.05 mm Hg = P
Remember that for a gaseous solution
(homogeneous mixture), the total pressure of
the solution is the sum of the partial pressures.
(Whos law is that?)
Therefore
P
total
= P
solvent
+ P
solute

VAPOR PRESSURE
LOWERING
This means that Raoults law can also be
applied to the vapor pressure of a solution with
a volatile solute. The total vapor pressure of
the mixture would be equal to the vapor
pressure created by the solvent added to the
vapor pressure created by the volatile solute.

P
total
= P
solv

X
solv
+ P
solute

X
solute



VAPOR PRESSURE
LOWERING
WHAT ELSE DOES VAPOR
PRESSURE LOWERING
AFFECT?
In the diagram notice
that the vapor pressure
lowers when a solvent
is mixed with a
nonvolatile solute.
The P
solv
increases
as the temperature
increases; similarly, the
P
solv
increases as the
temperature increases.
This means that the
lowering of the vapor
pressure leads to a
higher boiling point of
the solution.
Vapor Pressure
(mm Hg)
Temperature (C)
Solvent + Solute
Solvent
P
Definition:
The boiling point of a solution is greater than
the boiling point of the pure solvent because
the solution (which has a lower vapor
pressure) will need to be heated to a higher
temperature in order for the vapor pressure to
become equal to the external pressure (i.e.,
the boiling point).
BOILING POINT ELEVATION
The boiling point elevation, T
b
, is the
difference between the higher boiling point of
the solution and the boiling point of the pure
solvent.

T
b
= T
b
T
b

BOILING POINT ELEVATION
Boiling point
elevation
Boiling point
of solution
Boiling point of
pure solvent
The boiling point elevation, T
b
, is directly
proportional to the molality of the solute.

T
b
= k
b
m
solute
BOILING POINT ELEVATION
Boiling point
elevation
molal boiling point
elevation constant
molality of
the solute
MOLAL BOILING POINT
ELEVATION CONSTANT
Each solvent has a
different boiling
point constant.
Solvent
T
b
of
pure
solvent
(C)
k
b

(C/m)
Water 100.00 +0.5121
Benzene 80.10 +2.53
Camphor 207.4 +5.611
Chloroform 61.70 +3.63
A solution was made up of eugenol, C
10
H
12
O
2
, in diethyl ether. If
the solution was 0.575 m eugenol in ether, what was the boiling
point of the solution? The boiling point of pure ether is 34.6C
and the boiling-point-elevation constant is 2.02 C/m.
BOILING POINT ELEVATION
T
b
= k
b
m
solute
T
b
= T
b
T
b

Solute
Solve
nt
T
b
T
b
= 34.6C
k
b
= 2.02 C/m
m = 0.575 m
T
b
= ??
k
b
m
solute
= T
b
= T
b

T
b

(2.02 C/m)(0.575 m) = T
b

(34.6C)
35.8C = T
b

antifreeze, cocoa, gasoline and ethanol,
salted pasta water (just kidding)
BOILING POINT ELEVATION
Addition of a nonvolatile solute to the volatile
solvent increases the attractions (and lowers
the vapor pressure). This means that the
particles are closer together so a lower
temperature allows them to freeze.
FREEZING POINT
DEPRESSION
The freezing point depression, T
f
, is the
difference between the higher freezing point of
the pure solvent and the freezing point of the
solution.

T
f
= T
f
T
f

FREEZING POINT
DEPRESSION
Freezing point
depression
Freezing point
of pure solvent
Freezing point
of solution
The freezing point depression, T
f
, is directly
proportional to the molality of the solute.

T
f
= k
f
m
solute
FREEZING POINT
DEPRESSION
Freezing point
depression
molal freezing
point depression
constant
molality of
the solute
MOLAL FREEZING POINT
DEPRESSION CONSTANT
Each solvent has a
different freezing
point constant.
Solvent
T
f
of
pure
solvent
(C)
k
b

(C/m)
Water 0.0 +1.86
Benzene 5.50 +5.12
Camphor 179.95 +39.7
A solution was made up of 0.575 m eugenol, C
10
H
12
O
2
, in diethyl
ether. What was the freezing point of the solution? The freezing
point of pure ether is -116.3C and the freezing-point-depression
constant is
1.79 C/m.
FREEZING POINT
DEPRESSION
T
f
= k
f
m
solute
T
f
= T
f
T
f

Solute
Solve
nt
T
f
T
f
= 116.3C
k
f
= 1.79C/m
m = 0.575 m
T
f
= ??
k
f
m
solute
= T
f
= T
f

T
f

(1.79C/m)(0.575 m) = (116.3C)
T
f

117.3C = T
b

antifreeze (HEAT), salt on icy roads,
making ice cream, Crystal Lake freezes
before the pond in Veterans Acres
FREEZING POINT
DEPRESSION
COLLIGATIVE PROPERTY
ANIMATION
Osmosis is the diffusion of small molecules
through a semi-permeable membrane.
Usually, osmosis is seen in the net movement
of the solvent from the pure solvent (low solute
concentration) to solution (high solute
concentration).
OSMOTIC PRESSURE
The membrane is
termed semi-
permeable because
small molecules such
as water or small ions
(Na
+
or K
+
) may pass
in either direction
through the
membrane.
OSMOTIC PRESSURE
The solute reduces the mole fraction of the
solvent in a solution. The lower the mole
fraction of solvent, the greater the net flow
of solvent molecules into the solution (and
greater osmotic pressure).
OSMOSIS
OSMOTIC PRESSURE
Osmotic pressure is the pressure necessary to just
stop osmosis. This is done by pressing on the
solution side to increase the movement of solvent
particles from the solution back into the pure
solvent.
Osmotic pressure is proportional to the
molar concentration of the solute.
OSMOTIC PRESSURE
H ( )
H= MRT
PV = nRT
P =
n
V
RT
Notice how this equation is
based on the ideal gas
law:
Osmotic
pressure
Molarity of
the solute
Dextran, a polymer of glucose units, is produced by bacteria
growing in sucrose solutions. Solutions of dextran in water have
been used as a blood plasma substitute. What is the osmotic
pressure (in mmHg) at 21C of a solution containing 1.50 g of
dextran dissolved in 100.0 mL of aqueous solution, if the average
molecular weight of the dextran is 4.0 x 10
4
amu?
OSMOTIC PRESSURE
Solute
Solvent =
H
2
O
H
H= MRT
H= MRT
1.50g 1mol
4.0x10
4
g
= 3.75x10
5
mol
M =
3.75x10
5
mol
0.1000L
= 3.75x10
4
M
H = 3.75x10
4
M
( )
0.0821
atm-L
mol-L
( )
294K ( )
H = 0.00905atm = 6.9mmHg
reverse osmosis, vinegar and eggs, water
transportation in plants, blood pressure
(normal osmotic pressure when compared
to pure water), dialysis of cell walls,
desalinating ocean water
OSMOTIC PRESSURE
When a nonelectrolyte solute dissolves in a
solvent, it dissolves without separating into
ions.

Like methanol dissolving in water
CH
3
OH(l) CH
3
OH(aq)
Nonelectrolyte Solutes

When an electrolyte solute dissolves in a


solvent, it does separate into ions.

Like sodium sulfate dissolving in water
Na
2
SO
4
(s) 2 Na
+
(aq) + 1 SO
4
2
(aq)
Electrolyte Solutes

Since colligative properties depend on the


number of solute particles, not the identity
of the solute, an electrolyte influences those
properties more than a nonelectrolyte.

A 1.0 M sodium sulfate solution creates how many
particles?
Na
2
SO
4
(s) 2 Na
+
(aq) + 1 SO
4
2
(aq)
Electrolyte Solutes

2 + 1 = 3 particles
A strong electrolyte, such as Na
2
SO
4
, will
dissolve 100 %, creating one particle for
each dissociated ion.
These particles are called the vant Hoff
factor, i.

What is i for potassium phosphate?
Electrolyte Solutes

K
3
PO
4
(s) 3 K
+
(aq) + 1 PO
4
3
(aq)

4
A weak electrolyte, such as Ag
3
PO
4
, will
NOT dissolve 100 %. This means that
fewer particles will be able to influence the
colligative properties.

What is i for silver phosphate?
Electrolyte Solutes

Ag
3
PO
4
(s) 3 Ag
+
(aq) + 1 PO
4
3
(aq)

<4
How does this change the colligative
properties?


Electrolyte Solutes
Vapor Pressure
Lowering
Boiling Point Elevation
Freezing Point
Depression
Osmotic Pressure

P
1
= X
1
P
1
o
=
moleSolvent
moleSolvent + (i)moleSolute
|
\

|
.
|
P
1
o

AT
b
= k
b
- m- i = T
b
T
b
o

AT
f
= k
f
- m- i = T
f
o
T
f
H= iMRT