Colligative Properties

Properties that depend on the

PROPERTIES OF number of dissolved particles -- not
SOLUTIONS on the identity of the particle.

Vapor Pressure
These Properties Include of a solution containing a nonvolatile,
nonelectrolyte solute in water @ 25˚
25˚C

vapor pressure lowering Mol Fraction Vapor Pressure Mol Fraction Vapor Pressure
(solvent) (mmHg) (solvent) (mmHg)
boiling point elevation 1.0 23.6 0.5 11.8
freezing point depression 0.9 21.24 0.4 9.44
osmotic pressure
0.8 18.88 0.3 7.08

0.7 16.52 0.2 4.72

0.6 14.16 0.1 2.36

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Vapor Pressure Lowering Psolution = (Χ
(Χsolvent) (P
(Posolvent)

The presence of a nonvolatile solute Psolution = observed vapor pressure

lowers the vapor pressure of a of the solvent in the
solvent. solution
Χsolvent = mole fraction of solvent
Posolvent = vapor pressure of the
pure solvent
FOR AN IDEAL SOLUTION!

2
 Calculate the expected vapor pressure at 25 °C for
a solution prepared by dissolving 97.4 g of
common table sugar (sucrose, MM = 342 ) in 453
mL of water.
The vapor pressure of a solution is
directly proportional to the mole
fraction of solvent present.

Calculate the expected vapor pressure at 25 °C for

a solution prepared by dissolving 97.4 g of
common table sugar (sucrose, MM = 342 g mol-1) in
453 mL of water.
We will use Raoult's law in the form If the solute ionizes, the number of
Psoln = χH OP°H O
ions affects vapor pressure.
2 2
We need to determine the mol fraction of water
97.4 g (1 mol/342 g mol-1) = 0.285 mol sucrose
453 mL (1 g/1 mL) (1 mol/18 g mol-1) = 25.2 mol H2O
The moles of solute must be
χH O = 25.2 mol/(25.2 mol + .285 mol) = .989
2 multiplied by the number of ions the
The vapor pressure of water at 25 ˚C is 23.76 mm Hg
(Appendix C in Brown & LeMay). given solute breaks into.
Psoln = .989 (23.76 mm) = 23.5 mm of Hg

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 Exercise 5 Calculating the
An ideal solution is a solution that Vapor Pressure of a Solution
obeys Raoult’
Raoult’s Law. Calculate the expected vapor pressure
There is no such thing. at 25°C for a solution prepared by
dissolving 158.0 g of common table
In very dilute solutions, Raoult’
Raoult’s
sugar (sucrose, molar mass = 342.3
Law works fairly well. Solutions are
g/mol) in 643.5 cm3 of water.
most ideal when the solute and the
solvent are very similar.

Solution

At 25°C, the density of water is = 23.46 torr

0.9971 g/cm3 and the vapor
pressure is 23.76 torr.
torr.

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 Exercise 6 Calculating the
Vapor Pressure of a Solution Solution
Containing Ionic Solute
= 22.1 torr
Predict the vapor pressure of a
solution prepared by mixing 35.0 g
solid Na2SO4 (molar mass = 142
g/mol) with 175 g water at 25°C.
The vapor pressure of pure water at
25°C is 23.76 torr.
torr.

We can find the molecular Boiling Point Elevation

weight of a solute by using the
vapor pressure of a solution.
Because vapor pressure is lowered
χsolvent = mol solvent/(mol solute + mol solvent) by the addition of a nonvolatile
mol solute + mol solvent = mol solvent / χsolvent
solute, boiling point is increased.
mol solute = (mol solvent / χsolvent ) - mol solvent

MM solute = g solute/mol solute

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 ΔT = Kb x msolute x i

Kb = molal boiling point elevation

constant (for water = 0.51 ˚C/m)
C/m)
i = van’
van’t Hoff factor
m = concentration in molality
ΔT = change in temperature

Freezing Point Depression

Freezing is the temperature at A solution does not have a sharply

which the vapor pressure of the solid defined freezing point.
and the liquid are equal. If the vapor
pressure of the liquid is lowered, the Useful for separation purposes in
freezing point decreases. This is why fractional crystallization.
NaCl and CaCl2 are used on icy roads
and sidewalks.

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 ΔT = Kf x msolute x i

Solute concentration must be low

Kf = molal freezing point depression
(0.10m).
constant (for water = 1.86 ˚C/m)
C/m)
Add 6 qts.
qts. of antifreeze to 12 qts.
qts.
Disadvantage--compound must be
cooling system in order to lower the
nonvolatile and stable at the boiling
boiling
FP to -34°F and raise the BP to
point.
+226° F.

Example

Still used widely. Calculate the freezing point and

boiling point of a solution of 100. g
Remember that you are looking for ethylene glycol (C2H6O2) in 900. g
grams/mole! of water.

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Exercise 8 Calculating the
Molar Mass by Boiling-Point
Elevation
Calculate the molar mass of
A solution was prepared by dissolving glucose.
18.00 g glucose in 150.0 g water.
The resulting solution was found to Glucose is a molecular solid that is
have a boiling point of 100.34°C. present as individual molecules in
solution.

Exercise 9 Freezing-
Solution
Point Depression
= 180 g/mol What mass of ethylene glycol (C2H6O2,
molar mass = 62.1 g/mol), the main
component of antifreeze, must be added
to 10.0 L water to produce a solution for
use in a car’
car’s radiator that freezes at
-10.0°F (-23.3°C)? Assume the density
of water is exactly 1 g/mL.
g/mL.

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 Exercise 10 Determining
Solution Molar Mass by Freezing-
Point Depression
= 7.76 X 103 g (or 7.76 kg)
A chemist is trying to identify a
human hormone, which controls
metabolism, by determining its
molar mass.

Solution

A sample weighing 0.546 g was = 776 g/mol

dissolved in 15.0 g benzene, and
the freezing-point depression was
determined to be 0.240° C.

Calculate the molar mass of the

hormone.

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 Semipermeable
Membrane
Membrane which
OSMOTIC PRESSURE allows solvent but
not solute molecules
to pass through
(small molecules can
pass but large ones
cannot).

Osmosis
Osmosis occurs when solvent
molecules move through a
The passage of solvent into solution
semipermeable membrane from a
through a semipermeable membrane.
region of lower solute concentration
to a region of higher solute
concentration. It is driven by the
need nature has to establish an
equilibrium.

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Osmotic Pressure-(π
Pressure-(π)

The pressure that must be applied The osmotic pressure of a solution is

to a solution to prevent the net proportional to the number of solute
movement of water from solvent to particles in a given volume of
solution (osmosis). solution, that is, to the molarity.

π = MRTi or π = nRT x i
V
The equation is similar to the ideal
gas law since both relate the π = osmotic pressure in atm
M = molarity of the solution
pressure of a system to its
R = 0.08206 L-atm/K-mol
concentration and temperature.
T = temperature in Kelvin
i = van’
van’t Hoff factor

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The use of osmotic pressure
calculations for determining the
molecular mass of an unknown Ideal for measuring molar masses
substance is more accurate than the of large molecules of biological
use of freezing point depression or importance.
boiling point elevation data because a
small concentration of solute
produces a relatively large osmotic
pressure.

Example

The concentration of hemoglobin in Assume that a solution contains 15g

blood is roughly 15g/100mL of of hemoglobin dissolved in water to
solution. make 100 mL of solution and that
the osmotic pressure of this solution
is found to be 0.050 atm at 25°
25°C.

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What is the molecular mass of
hemoglobin?

(The osmotic pressure of a 1 m

solution at 25°
25°C is 24.45 atm.)
atm.)

Exercise 11 Determining
Molar Mass from Osmotic
Pressure
The osmotic pressure of this
To determine the molar mass of a solution was found to be 1.12 torr
certain protein, 1.00 X 10-3 g of it at 25.0°C.
was dissolved in enough water to
make 1.00 mL of solution. Calculate the molar mass of the
protein.

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 Exercise 12 Isotonic
Solution
Solutions
= 1.66 X 104 g/mol What concentration of sodium
chloride in water is needed to
produce an aqueous solution
isotonic with blood (Β
(Β = 7.70 atm at
25°C)?

Exercise 13
Solution
Osmotic Pressure
= 0.158 M The observed osmotic pressure for
a 0.10 M solution of Fe(NH4)2(SO4) 2
at 25°C is 10.8 atm.
atm.

Compare the expected and

experimental values for i.

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Solution

Expected = 5
APPLICATIONS OF
Experimental = 4.4 OSMOSIS

Dialysis

A phenomenon in which a Kidney dialysis

semipermeable membrane allows is one of most
transfer of both solvent molecules important
and small solute molecules and applications.
Waste
ions. Occurs in walls of most
molecules move into the “wash”
wash”
plant and animal cells.
solution and filter the blood.

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Isotonic Solution Hypertonic

Solution has
higher osmotic
pressure (cells
bathed in a hypertonic solution
would shrivel –crenation).
crenation). Treating
Solutions that have the same the surface of food with salt causes
osmotic pressure. (Ex. IV fluids) this to happen to bacteria.

Hypotonic Reverse Osmosis

Solution has The process occurring when the

lower osmotic high external pressure on a solution
pressure (cells causes a net flow of solvent through
bathed in a a semipermeable membrane from
hypotonic the solution to the solvent.
solution would
burst—
burst—hemolysis).
hemolysis).

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 Colloids (also called
Colloidal Dispersions)
Used in desalination Thomas Graham, 1860--albumin,
(the membrane here starch, gelatin and glue diffuse only
acts as a “molecular very slowly and could not be
filter”
filter” to remove crystallized. He called these
solute particles). The need for this substances colloids.
process will probably increase as the “A suspension of tiny particles
need for drinkable water increases. in some medium.”
medium.”

The dispersed colloidal particles are A colloidal particle has a diameter

larger than a simple molecule but between 1 and 1000 nm and may
small enough to remain distributed contain many atoms, ions, or
and not settle out. molecules.

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Because of their small particle size, The particles stay suspended
colloids have an enormous total because of electrostatic repulsion.
surface area.
Hydrophobic/Hydrophilic ends

This process is
Coagulation, destruction of a colloid, important in
occurs by heating (particles collide so removal of soot
hard that they stick together) or by from smoke so
the addition of an electrolyte that air quality
(neutralizes ion layers). has improved
somewhat in
industrialized cities.

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Tyndall Effect Brownian Motion

The scattering of light by particles. A characteristic movement in which

the particles change speed and
Used to distinguish between a direction erratically (solvent
suspension and a true solution. molecules collide with the colloidal
particles).
A true solution has particles that are
too small to scatter light.

Examples of Some
Suspensions are temporary Common Colloids
solutions. They will settle eventually.
Foam- colloidal dispersion of a gas
Colloids will not do this.
dispersed in a liquid or solid (ex.
Whipped cream and marshmallows)
Solutions are permanent. Particles
are really small. Colloids lie in
Aerosol- colloidal dispersion of a
between solutions and suspensions!
liquid or solid dispersed in a gas (ex.
Fog and smoke)

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Emulsion- colloidal dispersion of a i = van’
van’t Hoff factor (moles of
electrolyte must be multiplied by
liquid dispersed in a solid or liquid
this)
(ex. Butter and milk) Number of moles particles in
solution/number of moles particles
Solution- colloidal dispersion of a dissolved.

solid dispersed in a liquid or solid

(ex. Paint or ruby)

There are
fewer solvent For instance, if we had 1 mole of
molecules on
NaCl as the solute, we would use 2
the surface to
moles of particles for our mole
escape.
fraction calculations.
This can be mathematically expressed
by Raoult’
Raoult’s Law:

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 The experimental
For nonelectrolytes,
nonelectrolytes, i= 1. value of i is often
less than the
For electrolytes, i = the number of
particles formed when one formula
expected value
unit of the solute dissolves in the of i because of
solvent. a phenomenon
called “ion pairing”
pairing”.

If hydrogen bonding occurs between

solute and solvent, vapor pressure is
Especially in concentrated solutions, less than expected. We call this a
oppositely charged ions can pair up negative deviation from Raoult’
Raoult’ s law.
and thus, we have fewer particles This can often be predicted when an
than expected. enthalpy of the solution formation is
large and negative (exothermic).

21
 A great example of this negative Both solute and solvent contribute
deviation is acetone and water. to the vapor pressure.

If the solute is more volatile than We call this a positive deviation

the solvent, the vapor pressure of from Raoult’
Raoult’s law.
the solution is higher than the vapor
pressure of the solvent. In this case, The enthalpy of solution for this
the molecules have a higher type of deviation is positive.
tendency to escape than expected. (endothermic)

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 Exercise 7 Calculating the
Vapor Pressure of a Solution
Containing Two Liquids
A solution is prepared by mixing
5.81 g acetone (C3H6O, molar mass
= 58.1 g/mol) and 11.9 g chloroform
(HCCl3, molar mass = 119.4 g/mol).
At 35°C, this solution has a total
(same as Dalton’s Law) vapor pressure of 260. torr.
torr.

Is this an ideal solution? Solution

The vapor pressures of pure acetone Not an ideal solution.

and pure chloroform at 35°C are 345
and 293 torr,
torr, respectively.

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Solutions in which both solute and
solvent are liquid and the liquids are
volatile, do not behave ideally.

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