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Colligative Properties of Solutions

are properties of solutions that depend solely


on the number of particles of solute and NOT
on their chemical identity.
vapor pressure
boiling point
freezing point
osmotic pressure

Vapor Pressure of a Solution


A solute that is nonvolatile is
one that has no measurable
vapor pressure.
We will study the effects of
nonvolatile solutes on the
properties of solutions.
The presence of a nonvolatile
solute causes the vapor
pressure of the solution to be
lower than the vapor pressure
of the pure solvent.

Vapor Pressure of a Solution


Raoults Law

The extent to which the vapor pressure of a


solvent is lowered by a nonvolatile solute is
given, for an ideal solution, by Raoults Law.
Vapor pressure of
the solution

Raoults Law

Psolvent over solution = XsolventPsolvent


Xsolvent is the mole fraction of the solvent.
Psolvent is the vapor pressure of the pure
solvent at the solution temperature.

Raoults Law Example:


Nonvolatile
Solute
What is the vapor pressure at 25C (room
temperature) of a solution made by adding
226 g (1 cup) sugar (C12H22O11) to 118.5 mL (
cup) of water?
Pwater over sugar soln = XwaterPwater
mol water =

118.5 mL x 0.99707 g x 1 mol


mL 18.015 g

mol sugar = 226 g x 1 mol


342.30 g
Xwater = 6.559 = 0.9085
7.2192

= 0.660 mol

= 6.559 mol

Raoults Law Example:


Nonvolatile Solute
What is the vapor pressure at 25C (room
temperature) of a solution made by adding 226 g
(1 cup) sugar (C12H22O11) to cup of water?
Pwater over sugar solution = XwaterPwater

from
Appendix B

Pwater over sugar solution = (0.9085) (23.76 torr)


= 21.59 torr
Adding sugar to the water lowered its vapor pressure.
Adding more sugar would lower it still more.

Raoults Law Example: Two


Volatile Components

What is the vapor pressure at 25C of 80-proof


alcohol (40% alcohol by volume)?

Alcohol: C2H5OH, MM = 46.07 g,


v.p.(25C) = 54.68 torr, density (25C) = 0.786 g/mL
Water: MM = 18.015 g, v.p.(25C) = 23.76 torr,
density (25C) = 0.997 g/mL
Apply Raoults Law to each volatile component.
By convention, the liquid component present in
larger volume is the solvent.

Raoults Law Example: Two


Volatile Components

What is the vapor pressure at 25C of 80-proof


alcohol (40% alcohol by volume)?
Raoults Law for the water:
Pwater over water/alcohol solution = XwaterPwater

Find Xwater: We need a volume for the solution,


dont we? Any volume will do! 100 mL is
convenient, though.
100 mL 40 mL alcohol = 60 mL water

Raoults Law Example: Two


Volatile Components
Pwater over water/alcohol solution = XwaterPwater

Find Xwater:
60 mL water x 0.997 g x 1 mol
mL
18.015 g
40 mL alcohol x 0.786 g x 1 mol
mL 46.07 g
Xwater = 3.321
3.321+0.682

= 0.8296

= 3.321 mol
= 0.682 mol

Raoults Law Example: Two


Volatile Components
Pwater over water/alcohol solution = XwaterPwater

Pwater over w/alc soln = 0.8296 (23.76 torr) = 19.71 torr


Palcohol over water/alc solution = XalcoholPalcohol
Xalcohol = 0.682
4.003

= 0.170

Palcohol over w/alc soln = 0.170 (54.68 torr) = 9.32 torr

Raoults Law Example: Two


Volatile Components
Pwater over water/alcohol solution = 19.71 torr
Palcohol over water/alcohol solution = 9.32 torr
Now use Daltons Law of Partial Pressures to find
the total vapor pressure of the solution:
Ptot = 19.71 + 9.32 = 29.0 torr

Boiling Point of a Solution


For water in an open container, the boiling
point is the temperature at which the vapor
pressure of water equals the prevailing
atmospheric pressure.
Our sugar solution at 25C has a lower vapor
pressure than water at 25C.
This means the temperature at which the
sugar solution boils will be higher (102.8C)
than the temperature at which water boils
(100.0C).

This is called boiling point elevation.

Boiling Point Elevation


The relationship between boiling point
elevation and the number of particles of
solute in the solution is given by
Tb = Kbm
where Tb = Tbp(solution) - Tbp(pure solvent)
Kb is the molal boiling-point-elevation constant
and is for the solvent.

m is the molality of particles from the solute.

Boiling Point Elevation


Now you can calculate the boiling point of our
sugar solution yourself (Kb of water is 0.51C/m):

Tb = Kbm
The molality of solute particles in our sugar solution is
the same as the molality of the sugar itself.
m = mol sugar = 0.660 mol sugar
kg water
0.11815 kg water
Tb = (0.51C/m) (5.586m)

= 5.586 m

2.8C = 2.8C
Tb = Tbp(solution) - Tbp(pure=solvent)
Tbp(solution) = 100.00C + 2.8C = 102.8C

Boiling Point Elevation - Electrolytes


Electrolytes dissolve in water to form
ions. Each ion is a solute particle.
Tb = Kbm
If we made our solution up with 0.660 mol of NaCl
instead of sugar, the boiling point elevation would
be different from that of sugar.
m = 0.660 mol salt = 1.32 mol ions
0.11815 kg water 0.11815 kg water

= 11.18 m

Boiling Point Elevation - Electrolytes


Electrolytes dissolve in water to form
ions. Each ion is a solute particle.
Tb = Kbm and m = 11.18
Tb = (0.51C/m) (11.18 m)

= 5.7C

Tb = Tbp(solution) - Tbp(pure solvent) = 5.7C


Tbp(solution) = 100.00C + 5.7C = 105.7C

Boiling Point Elevation - Electrolytes


Tb = Kbm
If we made our solution up with 0.660
mol CaCl2 instead of sugar or salt, the
boiling point elevation would be even
more, because CaCl2 dissolves in water
to release 3 ions per mol.

Freezing Point Depression


The addition of a nonvolatile solute
to a solution lowers the freezing
point of the solution relative to that
of the pure solvent.

Freezing Point Depression


The relationship between freezing point
depression and the number of particles of
solute in the solution is given by
Tf = Kfm

note the
difference!!

where Tf = Tfp(pure solvent) - Tfp(solution)


Kf is the molal freezing-point-depression
constant and is for the solvent.

m is the molality of particles from the solute.

Freezing Point Depression


We will now calculate the freezing point of our
sugar solution (Kf of water is 1.86C/m):

Tf = Kfm
m = mol sugar = 0.660 mol sugar = 5.586 m
kg water
0.11815 kg water
Tf = (1.86C/m) (5.586m) = 10.4C
Tf = Tfp(pure solvent) - Tfp(solution) = 10.4C
Tfp(solution) = 0.00C 10.4C = -10.4C

Freezing Point Depression


We will now calculate the freezing point of our
salt solution:

Tf = Kfm
m = mol ions = 1.32 mol ions
= 11.17 m
kg water 0.11815 kg water
Tf = (1.86C/m) (11.17m) = 20.8C
Tf = Tfp(pure solvent) - Tfp(solution) = 20.8C
Tfp(solution) = 0.00C 20.8C = - 20.8C
If we had used CaCl2, Tfp(solution) would be even
lower. Thats why CaCl2 is sometimes used to salt
icy sidewalks.

Boiling Point Elevation and Freezing


Point Depression
Adding a
nonvolatile
solute to a
solvent
raises its
boiling point
and lowers
its freezing
point.

Boiling Point Elevation and Freezing


Point Depression
Another
way to look
at things:
Adding a
nonvolatile
solute to a
solvent
expands its
liquid
range.

Finding the Molar Mass of a Solute from


Boiling Point Elevation or Freezing Point
Depression Measurement
Using either Tb

= Kbm or Tf = Kfm

If you know the mass of solute that is not an


electrolyte and the mass of solvent used to
make a solution, and
you can measure the freezing point
depression or boiling point elevation of the
solution,
you can calculate the molar mass of the
solute.

Finding the Molar Mass of a Solute from


Boiling Point Elevation or Freezing Point
Depression Measurement
Tf = Kfm = Kf mol solute
kg solvent
= Kf (mass solute)
(molar mass of solute)(kg solvent)
Rearranging the equation gives:
molar mass of solute = Kf (mass solute)
Tf (kg solvent)

Molar Mass from Boiling Point


Elevation Data Example

A solution of 0.64 g of adrenaline in 36.0 g of CCl 4


has a b.p. of 77.03C. a) What is the molar mass
of adrenaline? b) What is the f.p. of the solution?
CCl4: b.p. (760 torr) = 76.54C Kb = 5.02C/m
m.p. (760 torr) = -22.3C Kf = 29.8C/m
Tb = Kbm
Tb = 77.03 76.54 = 0.49C
m = Tb / Kb = 0.49C
5.02C/m

= 0.0976 m

Molar Mass from Boiling Point


Elevation Data Example

A solution of 0.64 g of adrenaline in 36.0 g of CCl 4 has a


b.p. of 77.03C. a) What is the molar mass of adrenaline?
b) What is the f.p. of the solution?
CCl4: b.p. (760 torr) = 76.54C Kb = 5.02C/m
m.p. (760 torr) = -22.3C Kf = 29.8C/m

Molar mass of adrenaline = (5.02C/m) (0.64 g)


0.49C (0.0360 kg)
= 182 g/mol
(really 180)

Molar Mass from Boiling Point


Elevation Data Example

A solution of 0.64 g of adrenaline in 36.0 g of CCl 4 has a


b.p. of 77.03C. a) What is the molar mass of adrenaline?

b) What is the f.p. of the solution?


CCl4: b.p. (760 torr) = 76.54C Kb = 5.02C/m
m.p. (760 torr) = -22.3C Kf = 29.8C/m

Tf = Kfm
Tf = 29.8C (0.0976 m) = 2.908C
m

Molar Mass from Boiling Point


Elevation Data Example

A solution of 0.64 g of adrenaline in 36.0 g of CCl 4 has a


b.p. of 77.03C. a) What is the molar mass of adrenaline?

b) What is the f.p. of the solution?


Tf = 29.8C (0.0976 m) = 2.908C
m
Tf =Tf (CCl4) - Tf(soln) = 2.908C
Tf(soln) = Tf(CCl4) - 2.908 = -22.3 - 2.908 = -25.2C

Osmotic Pressure
The last colligative property we
will study is osmotic pressure.
It is based on the tendency of
solvent molecules to move
toward an area of lesser
concentration.
This movement causes osmotic
pressure when the areas of
differing solvent concentration
are separated by a
semipermeable membrane.

Osmotic Pressure
Osmotic pressure is
the pressure that
must be applied to
the solution in order
to just stop the
movement of solvent
molecules into the
solution.

Osmotic Pressure
The equation relating
osmotic pressure () to
concentration is very
similar to the ideal gas
law

= MRT
M = molarity particles in
the solution
R = gas constant
T = temperature in K

Hypertonic Solutions
Osmotic pressure plays an important role in living
systems. For example, the membranes of red blood
cells are semipermeable.
When we eat too
much salt, the high
concentration of
salt in our plasma
makes it
hypertonic relative
to the inside of the
red blood cell and
causes water to
diffuse out of the
red blood cells.

A red blood cell in a


hypertonic solution shrinks.

Hypotonic Solutions
When we perspire
heavily and then
drink a lot of water
(not gatorade), the
low concentration
of salt in our
plasma makes it
hypotonic relative
to the inside of the
red blood cell and
causes water to
diffuse into the red
blood cells.

A red blood cell in a


hypotonic solution expands
and may burst.

Isotonic Solutions
When we lose a lot of fluids and have to replace them,
the ideal situation is to receive fluids that are neither
hypertonic nor hypotonic. Fluids that have the same
osmotic pressure are said to be isotonic.
The osmotic pressure of blood is 7.7 atm at 37C. What
concentration of saline solution (NaCl in sterile water) is
isotonic with blood at human body temperature?
Using M = /RT,
M = molarity of solute particles =
7.7 atm
0.08206 L-atm (310. K)
mol-K

. = 0.30 M

Molarity of NaCl for isotonic saline = 0.15 M


In mass percent, an isotonic saline solution is 0.9% NaCl.