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Chapter 12

Physical Properties
of Solutions
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 Solutions
A solution is a homogenous mixture of 2 or more substances.

The solute is(are) the substance(s) present in the smaller

amount(s).

The solvent is the substance present in the larger amount.

Table 12.1 Types of Solutions

State of Resulting
Component 1 Component 2 Examples
Solution
Gas Gas Gas Air
Gas Liquid Liquid Soda water (CO2 in water)
Gas Solid Solid H2 gas in palladium
Liquid Liquid Liquid Ethanol in water
Solid Liquid Liquid NaCl in water
Solid Solid Solid Brass (Cu/Zn), solder (Sn/Pb)

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 Saturation
A saturated solution contains the maximum amount of a solute
that will dissolve in a given solvent at a specific temperature.
An unsaturated solution contains less solute than the solvent has
the capacity to dissolve at a specific temperature.
A supersaturated solution contains more solute than is present
in a saturated solution at a specific temperature.
Sodium acetate crystals rapidly form when a seed crystal is
added to a supersaturated solution of sodium acetate.

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 Formation of a Solution
Three types of interactions in the solution process:
• solvent-solvent interaction
• solute-solute interaction
• solvent-solute interaction

Molecular view of the formation of solution

ΔH soln  ΔH1 + ΔH 2 + ΔH 3

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 “Like Dissolves Like”

CH3OH
C2H5OH

Two substances with similar intermolecular forces are likely to be soluble in

each other.

non-polar molecules are soluble in non-polar solvents

CCl4 in C6H6

polar molecules are soluble in polar solvents

C2H5OH in H2O

ionic compounds are more soluble in polar solvents

NaCl in H2O or NH3 (l)

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 Temperature and Solubility
Solid solubility and temperature

solubility increases with

increasing temperature

solubility decreases with

increasing temperature

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 Temperature and Solubility
O2 gas solubility and temperature

Gas solubility usually

decreases with
increasing temperature

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 Concentration Units
The concentration of a solution is the amount of solute
present in a given quantity of solvent or solution.

Molarity (M) or molar concentration, which is the number

of moles of solute per liter of solution.
moles of solute
M =
liters of solution

Molality (m) is the number of moles of solute dissolved

in 1 kg (1000 g) of solvent
moles of solute
m =
mass of solvent (kg)
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 Comparison of Concentration Units
• The advantage of molarity is that it is generally easier to
measure the volume of a solution.
For this reason, molarity is often preferred over molality.

• Molality is independent of temperature, because the

concentration is expressed in number of moles of solute and
mass of solvent.

• The volume of a solution typically increases with increasing

temperature, so that a solution that is 1.0 M at 25 °C may become
0.97 M at 45 °C because of the increase in volume on warming.

• This concentration dependence on temperature can significantly

affect the accuracy of an experiment. Therefore, it is sometimes
preferable to use molality instead of molarity.

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 What mass of KI is required to make 500 mL of
a 2.80 M KI solution?
M KI M KI
volume of KI solution moles KI grams KI

1L 2.80 mol KI 166 g KI

500 mL x x x = 232 g KI
1000 mL 1 L soln 1 mol KI

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 Concentration Units
The Percent by Mass: (also called percent by weight or weight
percent) is the ratio of the mass of a solute to the mass of the
solution, multiplied by 100 percent:
mass of solute
% by mass = x 100%
mass of solute + mass of solvent

=
mass of solute
x 100%
mass of solution

Mole Fraction (X): The mole fraction of a component of a

solution, say, component A, is written XA and is defined as
moles of A
XA =
sum of moles of all components

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 To convert one concentration unit of a solution
to another
Example:
Express the concentration of a 0.396 m glucose (C6H12O6) solution in molarity?
(density of solution = 1.16 g/mL)

0.396 m glucose (C6H12O6)

i.e., there is 0.396 mole of glucose in 1000 g of the solvent.
To calculate molarity; we need to determine the volume of
this solution.
First, we calculate the mass of the solution from the molar
mass of glucose:

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 The density of the solution is 1.16 g/mL
We can now calculate the volume of the solution in liters

The molarity of the solution is given by

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 What is the molality of a 5.86 M ethanol (C2H5OH)
solution whose density is 0.927 g/mL?
moles of solute moles of solute
m = M =
mass of solvent (kg) liters of solution

Assume 1 L of solution:
5.86 moles ethanol = 270 g ethanol
927 g of solution (1000 mL x 0.927 g/mL)
mass of solvent = mass of solution – mass of solute
= 927 g – 270 g = 657 g = 0.657 kg

moles of solute 5.86 moles C2H5OH

m = = = 8.92 m
mass of solvent (kg) 0.657 kg solvent

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 Pressure and Solubility of Gases
The solubility of a gas in a liquid is proportional to the
pressure of the gas over the solution (Henry’s law).
c is the concentration (M) of the dissolved gas
c = kH P P is the pressure of the gas over the solution
kH is a constant for each gas (mol/L•atm) that
depends only on temperature

low P high P

low c high c
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 Most gases obey Henry’s law, but there are some important
exceptions:

For example, if the dissolved gas reacts with water, higher

solubilities can result.
The solubility of ammonia is much higher than
expected because of the reaction

Carbon dioxide also reacts with water, as follows:

Another interesting example is the dissolution of

molecular oxygen in blood.

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 Colligative Properties of Nonelectrolyte Solutions

Colligative properties are properties that depend only on the

number of solute particles in solution and not on the nature of
the solute particles.

o The colligative properties are

 vapor-pressure lowering,
 boiling-point elevation,
 freezing-point depression,
 osmotic pressure.

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 Vapor-Pressure Lowering
0
P1 = X1 P1 0
P1 = vapor pressure of pure solvent

Raoult’s law X1 = mole fraction of the solvent

If the solution contains only one solute:

X1 = 1 – X2
P1 - P1 = DP = X2 P1
0 0
X2 = mole fraction of the solute

We see that the decrease in vapor pressure, DP, is directly

proportional to the solute concentration (measured in mole
fraction).

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 Partial Pressure and Mole Fraction

PA  X P 0
A A

PB  X P B B
0

PT  PA  PB
PT  X A PA0  X B PB0

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 Raoult’s Law
PT is greater than predicted by PT is less than predicted by
Raoult’s law Raoult’s law

Force Force Force Force Force Force

 &  &
A -B A -A B-B A -B A -A B-B
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 Fractional Distillation Apparatus

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 Boiling-Point Elevation
DTb = Tb – T b0
T 0b is the boiling point of the
pure solvent
T b is the boiling point of the
solution

Tb > T b0 DTb > 0

DTb = Kb m
m is the molality of the solution
Kb is the molal boiling-point
elevation constant (0C/m)
for a given solvent
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 Freezing-Point Depression
DTf = T 0f – Tf
0
T fis the freezing point of
the pure solvent
T f is the freezing point of
the solution

T 0f > Tf DTf > 0

DTf = Kf m
m is the molality of the solution
Kf is the molal freezing-point
depression constant (0C/m)
for a given solvent
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 What is the freezing point of a solution containing 478 g
of ethylene glycol (antifreeze) in 3202 g of water? The
molar mass of ethylene glycol is 62.01 g/mol.

DTf = Kf m Kf water = 1.86 0C/m

1 mol
478 g x
moles of solute 62.01 g
m = = = 2.41 m
mass of solvent (kg) 3.202 kg solvent

DTf = Kf m = 1.86 0C/m x 2.41 m = 4.48 0C

DTf = T f0 – Tf

Tf = T f0 – DTf = 0.00 0C – 4.48 0C = -4.48 0C

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 Osmotic Pressure (p)
Osmosis is the selective passage of solvent molecules through a porous
membrane from a dilute solution to a more concentrated one.
A semipermeable membrane allows the passage of solvent molecules
but blocks the passage of solute molecules.
Osmotic pressure (p) is the pressure required to stop osmosis.

concentrated
dilute

more

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 Osmotic Pressure (p)

High Low
P P

M is the molarity of the solution

p = MRT R is the gas constant
T is the temperature (in K)
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 A cell in an:

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 Summary - Colligative Properties of
Nonelectrolyte Solutions
Colligative properties are properties that depend only on the
number of solute particles in solution and not on the nature of the
solute particles.

Vapor-Pressure Lowering P1 = X1 P 01
Boiling-Point Elevation DTb = Kb m
Freezing-Point Depression DTf = Kf m
Osmotic Pressure (p) p = MRT
Using Colligative Properties to Determine Molar Mass
From the experimentally determined freezing-point depression or
osmotic pressure, We can calculate the molality or molarity of the
solution. Knowing the mass of the solute, we can readily determine
its molar mass.
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 Colligative Properties of Electrolyte
Solutions 1
0.1 m NaCl solution  0.1 m Na + ions & 0.1 m Cl ions

Colligative properties are properties that depend only on the number

of solute particles in solution and not on the nature of the solute
particles.

0.1 m NaCl solution → 0.2 m ions in solution

actual number of particles in soln after dissociation

vant Hoff factor  i  
number of formula units initially dissolved in soln

i should be
nonelectrolytes 1
NaCl 2
CaCl2 3

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 Colligative Properties of Electrolyte
Solutions 2
Boiling-Point Elevation ΔTb  iK b m
Boiling-Point Depression ΔTf = iK f m
Osmotic Pressure  p  p  iMRT

Table 12.3 The van’t Hoff Factor of 0.0500 M Electrolyte Solutions at 25°C

Electrolyte i (Measured) i (Calculated)

Surcose* 1.0 1.0
HCl 1.9 2.0
NaCl 1.9 2.0
MgSO4 1.3 2.0
MgCl2 2.7 3.0
FeCl3 3.4 4.0

*Source is a nonelectrolyte. It is listed here for comparison only.

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