Molality and Mole Fraction

 In Chapter 5 we introduced two

important concentration units.
1. % by mass of solute

mass of solute
% w/w =  100%
mass of solution
2. Molarity
moles of solute
M =
Liters of solution
 Molality and Mole Fraction

 Molality is a concentration unit

based on the number of moles of
solute per kilogram of solvent.
moles of solute
m
kg of solvent
in dilute aqueous solutions molarity and
molality are nearly equal
Molality and Mole Fraction
 Calculate the molarity and the molality of an aqueous
solution that is 10.0% glucose, C6H12O6. The density of the
solution is 1.04 g/mL. 10.0% glucose solution has several
medical uses. 1 mol C6H12O6 = 180 g
Molality and Mole Fraction
 Calculate the molality of a solution that contains 7.25 g of
benzoic acid C6H5COOH, in 2.00 x 102 mL of benzene,
C6H6. The density of benzene is 0.879 g/mL. 1 mol
C6H5COOH = 122 g
Molality and Mole Fraction
• Mole fraction is the number of moles of one component divided
by the moles of all the components of the solution
– Mole fraction is literally a fraction using moles of one
component as the numerator and moles of all the components
as the denominator.
• In a two component solution, the mole fraction of one
component, A, has the symbol XA.

number of moles of A
XA 
number of moles of A + number of moles of B
Molality and Mole Fraction

 The mole fraction of component B - XB

number of moles of B
XB 
number of moles of A + number of moles of B
Note that X A  X B  1
The sum of all the mole fractions must equal 1.00.
Molality and Mole Fraction
 What are the mole fractions of glucose and water in
a 10.0% glucose solution?
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.
Colligative Properties of Solutions
 There are four common types of colligative
properties:
1. Vapor pressure lowering

2. Freezing point depression

3. Boiling point elevation

4. Osmotic pressure
 Vapor pressure lowering is the key to all four of
the colligative properties.
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.
 Raoult’s Law models this effect in ideal solutions.
Lowering of Vapor Pressure and
Raoult’s Law
 This graph shows how the solution’s vapor pressure
is changed by the mole fraction of the solute, which
is Raoult’s law.
 Fractional Distillation
• Distillation is a technique used to
separate solutions that have two
or more volatile components with
differing boiling points.
• A simple distillation has a single
distilling column.
– Simple distillations give reasonable
separations.
• A fractional distillation gives
increased separations because of
the increased surface area.
– Commonly, glass beads or steel wool
are inserted into the distilling
column.
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 because the solution’s vapor pressure is
lowered as described by Raoult’s law.
• The solution’s temperature must be raised to make
the solution’s vapor pressure equal to the
atmospheric pressure.
 The amount that the temperature is elevated is
determined by the number of moles of solute dissolved
in the solution.
Boiling Point Elevation

 Boiling point elevation relationship

is:
Tb  K b m
where : Tb  boiling point elevation
m  molal concentrat ion of solution
K b  molal boiling point elevation constant
for the solvent
 Freezing Point Depression
 Relationship for freezing point depression is:
Tf  K f m
where: Tf  freezing point depression of solvent
m  molal concentration of soltuion
K f  freezing point depression constant for solvent
Freezing Point Depression
• Notice the similarity of the two
relationships for freezing point depression
and boiling point elevation.

 Tf  K f m vs.  Tb  K b m
• Fundamentally, freezing point depression and boiling
point elevation are the same phenomenon.
– The only differences are the size of the effect which is
reflected in the sizes of the constants, Kf & Kb.
• This is easily seen on a phase diagram for a solution.
Freezing Point Depression
 Boiling Point Elevation
 What is the normal boiling point of a 2.50 m glucose,
C6H12O6, solution?
Freezing Point Depression
 Calculate the freezing point of a solution that contains 8.50 g
of benzoic acid (C6H5COOH, MW = 122) in 75.0 g of
benzene, C6H6.
 Determination of Molecular Weight by
Freezing Point Depression

• The size of the freezing point depression depends

on two things:
1. The size of the Kf for a given solvent, which are
well known.
2. And the molal concentration of the solution
which depends on the number of moles of
solute and the kg of solvent.
• If Kf and kg of solvent are known, as is often the
case in an experiment, then we can determine # of
moles of solute and use it to determine the
molecular weight.
Determination of Molecular Weight by Freezing
Point Depression
 A 37.0 g sample of a new covalent compound, a
nonelectrolyte, was dissolved in 2.00 x 102 g of water. The
resulting solution froze at -5.58oC. What is the molecular
weight of the compound?
 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 sugar dissolves in water to produce one mole of
aqueous sugar molecules.
 One mole of NaCl dissolves in water to produce two moles
of aqueous ions:
• 1 mole of Na+ and 1 mole of Cl- ions
 Osmotic Pressure
• Osmosis is the net flow of a solvent
between two solutions separated by a
semipermeable membrane.
– The solvent passes 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
 Osmotic Pressure
 Osmosis is a rate controlled phenomenon.
• The solvent is passing from the dilute solution into the
concentrated solution at a faster rate than in opposite
direction, i.e. establishing an equilibrium.
 The osmotic pressure is the pressure exerted by a column of
the solvent in an osmosis experiment.

  MRT
where:  = osmotic pressure in atm
M = molar concentration of solution
L atm
R = 0.0821
mol K
T = absolute temperature
 Osmotic Pressure
 For very dilute aqueous solutions,
molarity and molality are nearly
equal.
Mm
  mRT
for dilute aqueous solutions only
 Osmotic Pressure
 Osmotic pressures can be very large.
• For example, a 1 M sugar solution has an osmotic pressure
of 22.4 atm or 330 p.s.i.
 Since this is a large effect, the osmotic pressure
measurements can be used to determine the molar masses of
very large molecules such as:
1. Polymers
2. Biomolecules like
 proteins
 ribonucleotides
Osmotic Pressure
 A 1.00 g sample of a biological material was dissolved in
enough water to give 1.00 x 102 mL of solution. The osmotic
pressure of the solution was 2.80 torr at 25oC. Calculate the
molarity and approximate molecular weight of the material.