Chapter

5B

Simple Mixtures
 Chemical Potentials of Liquids
• Francois Raoult- ratio of partial
vapour pressure of each component
to its vapour pressure as a pure
liquid, PA/P*A, approximately equal to
mole fraction of A in the liquid
mixture.
PA = xAP*A ….. Raoult’s Law
• Some mixtures obey Raoult’s law
very well, especially for components
with similar structure such as
benzene and methylbenzene.
• μA=μ*A + RT lnxA …….Chemical
potential for ideal
solution
• In ideal solutions the solute and
solvent obeys the Raoult’s law.
• William Henry discovered that for
real solutions at low
concentrations, although the
vapour pressure of the solute is
proportional to its mole fraction
(xB), the constant of
proportionality is not the vapour
pressure of the pure substance.
• PB= xBKB …… Henry law
• Mixtures for which solute B obeys
Henry’s law and solvent A obeys
Raoult’s law- ideal-dilute solution
 Solutions

• Solutions are homogeneous mixtures of two or

more pure substances.
• In a solution, the solute is dispersed uniformly
throughout the solvent.
 Solutions

The intermolecular forces

between solute and
solvent particles must be
strong enough to compete
with those between solute
particles and those
between solvent particles.
 How Does a Solution Form?

As a solution forms, the solvent pulls solute

particles apart and surrounds, or solvates, them.
How Does a Solution Form

If an ionic salt is
soluble in water, it is
because the ion-
dipole interactions are
strong enough to
overcome the lattice
energy of the salt
crystal.
 Energy Changes in Solution
• Simply put, three
processes affect the
energetics of the process:
Ø Separation of solute
particles
Ø Separation of solvent
particles
Ø New interactions between
solute and solvent
 Student, Beware!

Just because a substance disappears when it

comes in contact with a solvent, it doesn’t mean
the substance dissolved.
 Student, Beware!

• Dissolution is a physical change—you can get back the original

solute by evaporating the solvent.
• If you can’t, the substance didn’t dissolve, it reacted.
Types of Solutions

• Saturated
Ø Solvent holds as much
solute as is possible at
that temperature.
Ø Dissolved solute is in
dynamic equilibrium
with solid solute
particles.
 Types of Solutions

• Unsaturated
Ø Less than the
maximum amount of
solute for that
temperature is
dissolved in the
solvent.
 Types of Solutions

• Supersaturated
Ø Solvent holds more solute than is normally possible at
that temperature.
Ø These solutions are unstable; crystallization can usually
be stimulated by adding a “seed crystal” or scratching
the side of the flask.
 Factors Affecting Solubility

• Chemists use the axiom

“like dissolves like”:
Ø Polar substances tend to
dissolve in polar solvents.
Ø Nonpolar substances tend to
dissolve in nonpolar
solvents.
Factors Affecting Solubility

The more similar the

intermolecular
attractions, the more
likely one substance is
to be soluble in
another.
 Factors Affecting Solubility

Glucose (which has

hydrogen bonding) is
very soluble in water,
while cyclohexane
(which only has
dispersion forces) is
not.
 Factors Affecting Solubility

• Vitamin A is soluble in nonpolar compounds (like

fats).
• Vitamin C is soluble in water.
 Gases in Solution

• In general, the solubility

of gases in water
increases with
increasing mass.
• Larger molecules have
stronger dispersion
forces.
Gases in Solution

• The solubility of
liquids and solids does
not change
appreciably with
pressure.
• The solubility of a gas
in a liquid is directly
proportional to its
pressure.
 Henry’s Law
Sg = kPg
where
• Sg is the solubility of the
gas;
• k is the Henry’s law
constant for that gas in
that solvent;
• Pg is the partial pressure
of the gas above the
liquid.
Colligative Properties of Nonelectrolyte Solutions
Nonvolatile solutes lower the vapor pressure of a solvent
by an amount proportional to the solute mole fraction.

Vapor-Pressure Lowering

P1 = X1 P 0
1
P 10 = vapor pressure of pure solvent

Raoult’s law X1 = mole fraction of the solvent

If the solution contains only one solute:

X1 = 1 – X2
P 10 - P1 = DP = X2 P 10 X2 = mole fraction of the solute
13.6
 The Properties of Solutions
• Real solutions composed of particles for which A-A, A-B and B-
B interactions.
• Not only may there be enthalpy and volume changes when
liquids mix, but there may also be an additional contribution
to the entropy arising from the way in which the molecules of
one type might cluster together instead of mingling freely
with the others.
• If the enthalpy change is large and positive or if the entropy
change is adverse (because of a reorganization of the
molecules that results in an orderly mixture), then the Gibbs
energy might be positive for mixing.
• In that case, separation is spontaneous and the liquids may be
immiscible.
 Colligative Properties of
Solutions
Not freezing when cold or boiling
when hot!
Changes in colligative properties depend only
on the number of solute particles present,
not on the identity of the solute particles.
Among colligative properties are
ØVapor pressure lowering
ØBoiling point elevation
ØMelting point depression
ØOsmotic pressure
 Colligative Properties
• Some of the properties of solutions do not
depend on the amount and type of solute
present in solution.
– Ie food coloring doesn’t affect the boiling point of
water (much)
• Properties that depend on the concentration
of solute particles but not on their identity are
called Colligative properties.
 Electrolyte and non Electrolyte
• Electrolytes are substances that dissolve in
water to give a solution that conducts an
electric current
– Sports drinks and salt water
– Ionic compounds are usually strong electrolytes
because they separate completely in water
– Covalent compounds can be strong, weak or non
electroyltes
• Non-electrolytes: a liquid or solid
substance that does not allow the flow of
an electric current, either in solution or in
its pure state, such as water or sucrose.
• Nonvolatile substance is one that has little
tendency to become a gas under existing
conditions
 Colligative Properties of
Electrolytes
Since these properties depend on the number of particles
dissolved, solutions of electrolytes (which dissociate in
solution) should show greater changes than those of
nonelectrolytes.
 Colligative Properties of
Electrolytes
However, a 1 M solution of NaCl does not show
twice the change in freezing point that a 1 M
solution of methanol does.
 Freezing point depression
The freezing point of a 1 molal solution of any
nonelectrolyte solute in water is found to be
1.86 degrees lower than the freezing point of
water.
Thus 1 mole of solute in 1 kg of water will equal
-1.86 degree C
• If you had 2 moles of solute in 1 kg of water
the freezing point would be -3.72
degree C.
• This is 1.86 X 2
• This 1.86 degree C/m is known as molal
freezing point constant (Kf)
• Molal Freezing point constant is the
freezing point depression of the solvent in a
1 molal solution of a nonvolatile, non
electrolyte solute.
 Kf for substances
• Each solvent has its own characteristic molal
freezing point constant.
• Kf is most accurate at 1 atm.
• Kf for water is -1.86, for Ether is -1.79 and
Acetic Acid -3.90
• The freezing point depression, ∆tf, is the
difference between the freezing points of
the pure solvent and a solution of a non
electrolyte in that solvent, and it is directly
proportional to the molal concentration of
the solution.
• ∆Tf=Kf*m
 Boiling Point Elevation and
Freezing Point Depression
Nonvolatile solute-
solvent interactions also
cause solutions to have
higher boiling points
and lower freezing
points than the pure
solvent.
 Freezing Point Depression
• The change in freezing
point can be found
similarly:
DTf = Kf ž m

• Here Kf is the molal

freezing point depression
constant of the solvent.

DTf is subtracted from the normal

freezing point of the solvent.
 Did you know?
• Some animals are able to survive freezing
temperatures by producing natural antifreezes,
substances that lower the freezing point of a liquid.
In many freeze-tolerant insects, the antifreezes are
alcohols and sugars.
• Examples are box turtles, painted turtles and garter
snakes, sugar maples and white spruce.
Sugar Maple
• Taking a sugar substance
from a tree can be used to
create maple syrup
• The maple syrup aqueous
solution boils at 219
degree F
• That is 7 degree higher
than water.
• Why?
 Boiling Point Elevation
The change in boiling point
is proportional to the
molality of the solution:
DTb = Kb ž m

where Kb is the molal

boiling point elevation
constant, a property of the
solvent.
DTb is added to the normal
boiling point of the solvent.
 Boiling Point Elevation and
Freezing Point Depression
Note that in both
equations, DT does not
DT b = Kb ž m
depend on what the
solute is, but only on
how many particles are
dissolved. DTf = Kf ž m
 Boiling point elevation
• The boiling point of a liquid is the temperature
at which the vapor pressure of the liquid is
equal to the prevailing atmospheric pressure.
• Vapor pressures of solutions containing
nonvolatile solute is lower than the vapor
pressure of the pure solvent.
• This means that more heat will be required
to raise the vapor pressure of the solution.
Thus, the boiling point of a solution is
higher than the boiling point of the pure
substance.

• The molal boiling point constant, Kb, is the

boiling point elevation of the solvent in a 1
molal solution of a nonvolatile, non
electrolyte solute.
 Boiling point elevation
• Boiling point elevation, ∆tb, is the difference between the
boiling points of the pure solvent and a nonelectrolyte
solution of that solvent, and it is directly proportional to the
molal concentration of the solution.
• ∆Tb=Kb*m
• The heterogeneous equilibrium
involved in the calculation of the
elevation of boiling point is between
A in the pure vapour and A in the
mixture, A being the solvent and B
an non-volatile solute
 Example
• What is the new freezing point of 200 mL of
water (Kf = -1.86 oC) if 195 g of sucrose
(C12H22O11) are added to it?
 195 g sucrose
= .570 moles
342 g

.570 moles
= 2.85 molal
.200 Kg

Now we can plug into ∆Tf=Kf*m

∆Tf=(-1.86oC) * (2.85 molal)

∆Tf= -5.3010C

This means the water will freeze 5.301oC below

its freezing point.
 Ways of
Expressing
Concentrations of
Solutions
 Mass Percentage

mass of A in solution
Mass % of A = ´ 100
total mass of solution
 Parts per Million and
Parts per Billion
Parts per Million (ppm)
mass of A in solution
ppm = ´ 106
total mass of solution

Parts per Billion (ppb)

mass of A in solution
ppb = ´ 109
total mass of solution
 Mole Fraction (X)

moles of A
XA =
total moles in solution

• In some applications, one needs the mole

fraction of solvent, not solute—make sure
you find the quantity you need!
 Molarity (M)

mol of solute
M=
L of solution

• Because volume is temperature dependent,

molarity can change with temperature.
 Molality (m)

mol of solute
m=
kg of solvent

Because both moles and mass do not

change with temperature, molality (unlike
molarity) is not temperature dependent.
Changing Molarity to Molality

If we know the density

of the solution, we
can calculate the
molality from the
molarity, and vice
versa.
Exercise
Solution
Exercise
Solution
Exercise
Solution
Solution
Assignment 2