Physical Properties of Solutions

Chapter 12
1

Learning Goals

Types of solutions
Molecular view of the solution process
Concentration units
Effect of temperature on solubility
Effect of pressure on solubility
Colligative properties

Properties of a solution are substantially different to

those of the solvent

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
Very wide definition!

We will focus on those solutions in which at least one of the

components is a liquid (typically water = aqueous solution)

Gas-Liquid
Liquid-Liquid
Solid-Liquid

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.

Molecular view of the formation of solution

Particles of solute dissolving in a solvent will replace
particles of solvent

The ease by which this happens depends on three main

types of interactions:
solvent-solvent interaction
solute-solute interaction
solvent-solute interaction
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Molecular view of the formation of solution

For simplicity, we can consider three steps:
Endothermic

Endothermic

DHsoln = DH1 + DH2 + DH3

The process can be
exothermic or
endothermic

Molecular view of the formation of solution

Exothermic (DHsoln 0) if solute-solvent interaction is
stronger than solute-solute and solvent-solvent
Endothermic (DHsoln 0) if solute-solvent interaction is
weaker than solute-solute and solvent-solvent

The process of solution occurs because of the higher

disorder of the solution compared to the solvent and the
solute.

Solubility
Maximum amount of solute that can be dissolved in
a solvent at a specific temperature
Factors affecting solubility:
Intermolecular forces
Temperature
Pressure

10

Intermolecular Forces and Solubility

Two substances with similar intermolecular forces are likely
to be soluble in each other.
H2O

CH3CH2OH

Ethanol

Hydrogen bond

Water

Two liquids are miscible if they are soluble in each other

at any proportion

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Intermolecular Forces and Solubility

like dissolves like

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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Example 12.1
Predict the relative solubilities in the following cases:
(a) Bromine (Br2) in benzene (C6H6, = 0 D) and in water
( = 1.87 D)
(b) KCl in carbon tetrachloride (CCl4, = 0 D) and in liquid
ammonia (NH3, = 1.46 D)
(c) formaldehyde (CH2O) in carbon disulfide (CS2, = 0 D) and
in water

Example 12.1
Strategy In predicting solubility, remember the saying: Like
dissolves like. A nonpolar solute will dissolve in a nonpolar
solvent; ionic compounds will generally dissolve in polar
solvents due to favorable ion-dipole interaction; solutes that can
form hydrogen bonds with the solvent will have high solubility in
the solvent.
Solution
(a) Br2 is a nonpolar molecule and therefore should be more
soluble in C6H6, which is also nonpolar, than in water. The
only intermolecular forces between Br2 and C6H6 are
dispersion forces.

Example 12.1
(b) KCl is an ionic compound. For it to dissolve, the individual
K+ and Cl ions must be stabilized by ion-dipole interaction.
Because CCl4 has no dipole moment, KCl should be more
soluble in liquid NH3, a polar molecule with a large dipole
moment.
(c) Because CH2O is a polar molecule and CS2 (a linear
molecule) is nonpolar, the forces between molecules of
CH2O and CS2 are dipole-induced dipole and dispersion.
On the other hand, CH2O can form hydrogen bonds with
water, so it should be more soluble in that solvent.

Temperature and Solubility

Solid solubility and temperature

solubility increases with

increasing temperature

solubility decreases with

increasing temperature

16

Temperature and Solubility

No correlation between the sign of DHsoln and solubility
can be established

CaCl2 : Process of solution exothermic

NH4NO3 : Process of solution endothermic

Solubility

Temperature

17

Fractional crystallization is the separation of a mixture of

substances into pure components on the basis of their differing
solubilities.
Suppose you have 90 g KNO3
contaminated with 10 g NaCl.
Fractional crystallization:

1. Dissolve sample in 100 mL of

water at 600C
2. Cool solution to 00C

3. All NaCl will stay in solution

(s = 34.2g/100g)
4. 78 g of PURE KNO3 will
precipitate (s = 12 g/100g).
90 g 12 g = 78 g
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Temperature and Solubility

O2 gas solubility and temperature

solubility usually
decreases with
increasing temperature

Direct consequences in
thermal pollution

19

Pressure and Solubility

Pressure will have no effect on the solubility of liquids and
solids

Pressure will affect the solubility of gases

20

Pressure and Solubility of Gases

The solubility of a gas in a liquid is proportional to the
pressure of the gas over the solution (Henrys law).

c = kP

(If several gases are present, P

is the partial pressure)

c is the concentration (M) of the dissolved gas

P is the pressure of the gas over the solution

k is a constant for each gas (mol/Latm) that
depends only on temperature
21

Pressure and Solubility of Gases

From a molecular point of view, more or less gas will
dissolve depending on the frequency of collisions with the
surface of the liquid.

low P

high P

low c

high c

22

Example 12.6
The solubility of nitrogen gas at 25C and 1 atm of nitrogen
partial pressure is
6.8 104 mol/L.
What is the concentration (in molarity) of nitrogen dissolved in
water under atmospheric conditions?
The partial pressure of nitrogen gas in the atmosphere is
0.78 atm.

Example 12.6
Strategy The given solubility enables us to calculate Henrys
law constant (k), which can then be used to determine the
concentration of the solution.
Solution The first step is to calculate the quantity k in
Equation (12.3):

Example 12.6
Therefore, the solubility of nitrogen gas in water is

The decrease in solubility is the result of lowering the pressure

from 1 atm to 0.78 atm.
Check
The concentration ratio [(5.3 104 M/6.8 104 M) = 0.78]
should be equal to the ratio of the pressures
(0.78 atm/1.0 atm = 0.78).

Concentration Units
The concentration of a solution is the amount of solute
present in a given quantity of solvent or solution.
Percent by Mass
mass of solute
x 100%
% by mass =
mass of solute + mass of solvent
mass of solute x 100%
=
mass of solution
Mole Fraction (X)

Frequently used when

working with gases

moles of A
XA =
sum of moles of all components

26

Example 12.2
A sample of 0.892 g of potassium chloride (KCl) is dissolved in
54.6 g of water.
What is the percent by mass of KCl in the solution?

Example 12.2
Strategy We are given the mass of a solute dissolved in a
certain amount of solvent. Therefore, we can calculate the
mass percent of KCl using Equation (12.1).
Solution We write

Concentration Units
Molarity (M)

M =

moles of solute

Easier to measure

liters of solution

Molality (m)
m =

moles of solute
mass of solvent (kg)

Does not depend on

the temperature

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Example 12.3
Calculate the molality of a sulfuric acid solution containing
24.4 g of sulfuric acid in 198 g of water.
The molar mass of sulfuric acid is 98.09 g.

Example 12.3
Strategy To calculate the molality of a solution, we need to
know the number of moles of solute and the mass of the
solvent in kilograms.
Solution The definition of molality (m) is

First, we find the number of moles of sulfuric acid in 24.4 g of

the acid, using its molar mass as the conversion factor.

Example 12.3
The mass of water is 198 g, or 0.198 kg. Therefore,

Example 12.4
The density of a 2.45 M aqueous solution of methanol (CH3OH)
is 0.976 g/mL. What is the molality of the solution? The molar
mass of methanol is 32.04 g.

Example 12.4
Strategy To calculate the molality, we need to know the
number of moles of methanol and the mass of solvent in
kilograms. We assume 1 L of solution, so the number of
moles of methanol is 2.45 mol.

Example 12.4
Solution Our first step is to calculate the mass of water in 1 L
of the solution, using density as a conversion factor. The total
mass of 1 L of a 2.45 M solution of methanol is

Because this solution contains 2.45 moles of methanol, the

amount of water (solvent) in the solution is

Example 12.4
The molality of the solution can be calculated by converting
898 g to 0.898 kg:

Example 12.5
Calculate the molality of a 35.4 percent (by mass) aqueous
solution of phosphoric acid (H3PO4).
The molar mass of phosphoric acid is 97.99 g.

Example 12.5
Strategy In solving this type of problem, it is convenient to
assume that we start with a 100.0 g of the solution. If the mass
of phosphoric acid is 35.4 percent, or 35.4 g, the percent by
mass and mass of water must be 100.0% 35.4% = 64.6%
and 64.6 g.
Solution From the known molar mass of phosphoric acid, we
can calculate the molality in two steps, as shown in Example
12.3. First we calculate the number of moles of phosphoric
acid in 35.4 g of the acid

Example 12.5
The mass of water is 64.6 g, or 0.0646 kg. Therefore, the
molality is given by

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 10

Boiling-Point Elevation

DTb = Kb m

Freezing-Point Depression

DTf = Kf m

40

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
If the solute of a solution is non-volatile, the vapor pressure
of the solution is lower than that of the solvent.

P1 = X1 P

0
1

P 10 = vapor pressure of pure solvent

at a given temperature

Raoults law

X1 = mole fraction of the solvent

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Vapor-Pressure Lowering
If the solution contains only one solute:
X1 = 1 X2

P 10 - P1 = DP = X2 P 10

X2 = mole fraction of the solute

Why?

The disorder of a solution is greater than that of the

solvent. The difference of order between the solution
and the vapor is lower than between the solvent and
the vapor
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Example 12.7
Calculate the vapor pressure of a solution made by dissolving
218 g of glucose (molar mass = 180.2 g/mol) in 460 mL of water
at 30C.
What is the vapor-pressure lowering?
The vapor pressure of pure water at 30C is 31.82 mmHg.
Assume the density of the solvent is 1.00 g/mL.

Example 12.7
Strategy We need Raoults law [Equation (12.4)] to determine
the vapor pressure of a solution. Note that glucose is a
nonvolatile solute.
Solution The vapor pressure of a solution (P1) is

First we calculate the number of moles of glucose and water in

the solution:

Example 12.7
The mole fraction of water, X1, is given by

From Table 5.3, we find the vapor pressure of water at 30C to

be 31.82 mmHg. Therefore, the vapor pressure of the glucose
solution is
P1 = 0.955 31.82 mmHg
= 30.4 mmHg
Finally, the vapor-pressure lowering (DP) is
(31.82 30.4) mmHg, or 1.4 mmHg.

If both components of the solution are volatile:

Raoults law
Ideal Solution

PT = PA + PB
PA = XA P A0
PB = XB P 0B
PT = XA P A0 + XB P B0
Ideal behavior when DHsoln = 0
46

PT is greater than
predicted by Raoults law

PT is less than
predicted by Raoults law

Force
Force
Force
< A-A & B-B
A-B

Force
Force
Force
> A-A & B-B
A-B

Positive deviation

Negative deviation

Fractional Distillation Apparatus

48

Boiling-Point Elevation
We said that vapor pressure of the
solution is lower than the solvent,
therefore, boiling point is higher.

DTb = Tb T b0
T b0 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
49

Freezing-Point Depression
DTf = T 0f Tf
T

Tf

is the freezing point of

the pure solvent
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
50

Why?
Qualitatively, to freeze energy must be removed from the
system to reduce the disorder and go from liquid to solid. The
solution is more disordered than the solvent, more energy
has to be removed.

51

Example 12.8
Ethylene glycol (EG), CH2(OH)CH2(OH), is a common
automobile antifreeze. It is water soluble and fairly nonvolatile
(b.p. 197C).
Calculate the freezing point of a solution containing 651 g of
this substance in 2505 g of water.
Would you keep this substance in your car radiator during the
summer?
The molar mass of ethylene glycol is 62.01 g/mole.

Example 12.8
Strategy This question asks for the depression in freezing
point of the solution.

The information given enables us to calculate the molality of the

solution and we refer to Table 12.2 for the Kf of water.
Solution To solve for the molality of the solution, we need to
know the number of moles of EG and the mass of the solvent in
kilograms.

Example 12.8
We fi nd the molar mass of EG, and convert the mass of the
solvent to 2.505 kg, and calculate the molality as follows:

From Equation (12.7) and Table 12.2 we write

Example 12.8
Because pure water freezes at 0C, the solution will freeze at
(0 7.79)C or -7.79C.
We can calculate boiling-point elevation in the same way as
follows:

Because the solution will boil at (100 + 2.2)C, or 102.2C, it

would be preferable to leave the antifreeze in your car radiator
in summer to prevent the solution from boiling.

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 10

Boiling-Point Elevation

DTb = Kb m

Freezing-Point Depression

DTf = Kf m

They can be used to calculate the molar mass of a

substance
56

The one that shows the most pronounced change

57

Example 12.10
A 7.85-g sample of a compound with the empirical formula C5H4
is dissolved in 301 g of benzene.
The freezing point of the solution is 1.05C below that of pure
benzene.
What are the molar mass and molecular formula of this
compound?

Example 12.10
Strategy Solving this problem requires three steps. First, we
calculate the molality of the solution from the depression in
freezing point.
Next, from the molality we determine the number of moles in
7.85 g of the compound and hence its molar mass.
Finally, comparing the experimental molar mass with the
empirical molar mass enables us to write the molecular formula.
Solution The sequence of conversions for calculating the
molar mass of the compound is

Example 12.10
Our first step is to calculate the molality of the solution. From
Equation (12.7) and Table 12.2 we write

Because there is 0.205 mole of the solute in 1 kg of solvent, the

number of moles of solute in 301 g, or 0.301 kg, of solvent is

Example 12.10
Thus, the molar mass of the solute is

Now we can determine the ratio

Therefore, the molecular formula is (C5H4)2 or C10H8

(naphthalene).

Colligative Properties of Electrolyte Solutions

0.1 m Na+ ions & 0.1 m Cl- ions

0.1 m NaCl solution

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
vant Hoff factor (i) =

0.2 m ions in solution

actual number of particles in soln after dissociation
number of formula units initially dissolved in soln

i should be
nonelectrolytes
NaCl
CaCl2

1
2
3

62

Colligative Properties of Electrolyte Solutions

Boiling-Point Elevation

DTb = i Kb m

Freezing-Point Depression

DTf = i Kf m

63

Colligative Properties of Electrolyte Solutions

The correlation is not exact because of the ion pair effect that
reduces the number of particles in solution, especially as the
concentration increases.

64