Chapter 13

Physical Properties of Solutions

Fourth
Edition
The content of these slides has been adapted from
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 Physical Properties of
CHAPTER
13
Solutions

13.1 Types of Solutions

13.2 The Solution Process
13.3 Concentration Units
13.4 Factors That Affect Solubility
13.5 Colligative Properties
13.6 Calculations Using Colligative Properties

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13.1 Types of Solutions

Topics
Types of Solutions

Learning Objectives
• Recognize the types of solutions according to their degree of saturation
and state of matter.
• Explain the energy changes associated with solution formation.
• Express the concentration of a solution with different units and
interconvert them.
• Describe how major factors affect the solubility.
• Recognize and explain how the concentration of a solute determines
certain physical properties of a solution.
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 13.1 Solutions
Solutions can be classified as “unsaturated”, “saturated”, or “supersaturated”
 Unsaturated can still dissolve more solute at a given temperature
 Saturated contains the maximum amount of solute that will dissolve in a specific solvent at a
specific T°C
 Supersaturated contains more dissolved solute than is present in a saturated solution and is
unstable

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 13.1 Types of Solutions

TABLE 13.1 Types of Solutions

Solute Solvent State of Resulting Solution Example
Gas Gas Gas* Air
Gas Liquid Liquid Carbonated water
Gas Solid Solid
Liquid Liquid Liquid Ethanol in water
Liquid Solid Solid Mercury in silver
Solid Liquid Liquid Saltwater
Solid Solid Solid Brass (Cu/Zn)

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13.2 The Solution Process

Topics
Intermolecular Forces and Solubility
The Driving Force for Dissolution

Learning Objectives
• Recognize the types of solutions according to their degree of saturation
and state of matter.
• Explain the energy changes associated with solution formation.
• Express the concentration of a solution with different units and
interconvert them.
• Describe how major factors affect the solubility.
• Recognize and explain how the concentration of a solute determines
certain physical properties of a solution.
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 13.2 The Solution Process
Intermolecular Forces and Solubility
When the solute dissolves in the solvent, molecules of the solute
disperse throughout the solvent. They are, in effect, separated
from one another and each solute molecule is surrounded by
solvent molecules—a process known as solvation.

The ease with which solute molecules are separated from one
another and surrounded by solvent molecules depends on the
relative strengths of three types of interactions:

1. Solute-solute interactions
2. Solvent-solvent interactions
3. Solute-solvent interactions
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13.2 The Solution Process

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13.2 The Solution Process

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13.2 The Solution Process

Solute-solute interactions: Energy is absorbed (positive H1) to

overcome intermolecular forces holding solute particles together
in a crystal.

Solvent-solvent interactions: Energy is absorbed (positive H2) to

overcome intermolecular forces between solvent molecules.

Solute-Solvent interactions: Energy is released (negative H3)

when solvent molecules cluster around solute particles and
solvate them.

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 13.2 The Solution Process
Intermolecular Forces and Solubility

exothermic
endothermic

The thermicity of the dissolving process is one factor that

influences solubility.

Dissolution (‫ )ذوبان‬tends to be encouraged when it is

exothermic and discouraged when it is endothermic.

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 13.2 The Solution Process
Intermolecular Forces and Solubility
Two substances with similar intermolecular forces are likely
to be soluble in each other – “like dissolves like”
• non-polar molecules are more soluble in non-polar solvents
CCl4 in C6H6
• polar molecules are more soluble in polar solvents
C2H5OH in H2O
• ionic compounds are more soluble in polar solvents
NaCl in H2O or NH3(l)
Two liquids are said to be miscible if they are completely
soluble in each other in all proportions.
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 13.2 The Solution Process
 The solution process is called “SOLVATION”.
 Polar solvents dissolve polar solutes and ionic compounds / Nonpolar solvents
dissolve nonpolar solutes.
 MISCIBLE liquids can form one homogeneous phase (solution) when mixed.
 IMMISCIBLE liquids Do NOT mix together to form a solution, they rather exist
as separate layers.

BEFORE Mixing AFTER Mixing

Octane (Nonpolar)

Aqueous solution of C8H18

CuSO4 (Polar) H2O C8H18
Carbon tetrachloride CCl4 CCl4
(Nonpolar)
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SAMPLE PROBLEM 13.1
Determine for each solute whether the solubility will be
greater in water, which is polar, or in benzene , which is
nonpolar:
(a) bromine
(b) sodium iodide
(c) carbon tetrachloride
(d) formaldehyde

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SAMPLE PROBLEM 13.1 Setup

Setup
(a) Bromine is a homonuclear diatomic molecule and is
nonpolar.
(b) Sodium iodide is ionic.

(c) (d)

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SAMPLE PROBLEM 13.1 Solution
Solution
(a) Bromine is more soluble in benzene.
(b) Sodium iodide is more soluble in water.
(c) Carbon tetrachloride is more soluble in benzene.
(d) Formaldehyde is more soluble in water.

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Worked Example Correlating Solubility and Chemical Structure
Pentane (C5H12) and 1-butanol (C4H9OH) are organic liquids with similar molecular masses but substantially
different solubility behavior. Which of the two would you expect to be more soluble in water? Explain.

Strategy
There are two ways to do this and every other problem in chemistry. One is to think things through to be sure
you understand what’s going on; the other is to plug numbers into a formula and hope for the best. The thinking
approach always works; the formula approach works only if you use the right equation. Let’s try both ways.
Worked Example Correlating Solubility and Chemical Structure
Pentane (C5H12) and 1-butanol (C4H9OH) are organic liquids with similar molecular masses but substantially
different solubility behavior. Which of the two would you expect to be more soluble in water? Explain.

Strategy
There are two ways to do this and every other problem in chemistry. One is to think things through to be sure
you understand what’s going on; the other is to plug numbers into a formula and hope for the best. The thinking
approach always works; the formula approach works only if you use the right equation. Let’s try both ways.

Solution
Pentane is a nonpolar molecule and is unlikely to have strong intermolecular interactions with polar water
molecules. 1-Butanol, however, has an –OH part just as water does and can form hydrogen bonds with water.
As a result, 1-butanol is more soluble in water.
13.2 The Solution Process

Ionic Compounds
 DO NOT dissolve in Nonpolar solvents (e.g., CCl4, Octane).

 They dissolve in water.

NaCl dissolution in water

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13.2 The Solution Process

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13.2 The Solution Process - Enthalpy

When ∆H3 > ∆H1 + ∆H2

 Solute–solvent interactions are

stronger than solute–solute or
solvent–solvent interactions.
 The process is exothermic.

example: CaCl2
ΔHsoln = − 81.3 [Link]-1

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13.2 The Solution Process - Enthalpy

When ∆H3 < ∆H1 + ∆H2

 Solute–solvent interactions are

weaker than solute–solute and
solvent–solvent interactions.
 The process is endothermic.

Example: NH4NO3
ΔHsoln = +25.7 [Link]-1

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13.2 The Solution Process - Enthalpy

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 13.2 The Solution Process

The Driving Force for Dissolution

Dissolution tends to be favored when the enthalpy change is
negative (exothermic).

Yet there are many substances that dissolve endothermically.

For example, ammonium nitrate,

There must be another factor that influences dissolution. This

other factor is the change in the system’s entropy.

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13.2 The Solution Process
So why does NH4NO3 dissolve?
There is an entropy increase for the solution process.

Solution #1

Solution #2

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 13.2 The Solution Process

Example of Entropy Increase (Gases)

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13.3 Concentration Units

Topics
Molality
Percent by Mass
Comparison of Concentration Units
Learning Objectives
• Recognize the types of solutions according to their degree of saturation
and state of matter.
• Explain the energy changes associated with solution formation.
• Express the concentration of a solution with different units and
interconvert them.
• Describe how major factors affect the solubility.
• Recognize and explain how the concentration of a solute determines
certain physical properties of a solution.
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13.3 Concentration Units

Moles of solute
Molarity (M) =
Liters of solution

Moles of component
Mole fraction (X) =
Total moles making up solution

Mass of component
Mass percent = x 100%
Total mass of solution

Moles of solute
Molality (m) =
Mass of solvent (kg)

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 13.3 Concentration Units

Comparison of Concentration Units

The advantage of molarity is that it is generally easier to
measure the volume of a solution, using precisely calibrated
volumetric flasks, than to weigh the solvent.

Molality, on the other hand, has the advantage of being

temperature independent.

Percent by mass is similar to molality in that it is independent

of temperature. Furthermore, we do not need to know the
molar mass of the solute to calculate the percent by mass.

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 SAMPLE PROBLEM

“Rubbing alcohol” is a mixture of isopropyl alcohol and water

that is 70 percent isopropyl alcohol by mass

Express the concentration of rubbing alcohol in

(a) Molarity
(b) Molality

Setup
The mass of a liter of rubbing alcohol is 790 g, and the molar
mass of isopropyl alcohol is 60.09 g/mol.

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 SAMPLE PROBLEM

Solution

(a)

Rubbing alcohol is 9.2 M and 39 m in isopropyl alcohol.

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 13.3 Concentration Units

Percent by Mass (also called percent by weight)

massof solute
solutemass percent= ×100%
massof solute+mass of solvent mass of solution

How to convert mass percent to parts per million, ppm?

1% = 10000 ppm

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 SAMPLE PROBLEM 13.2
Setup
A solution is made by dissolving 170.1 g of glucose in enough
water to make a liter of solution. The density of the solution is
1.062 g/mL.

Express the concentration of the solution in:

(a) Molality
(b) Percent by mass (part per hundred)
(c) Parts per million

Setup
The molar mass of glucose is 180.2 g/mol; the density of the
solution is 1.062 g/mL.
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SAMPLE PROBLEM 13.2 Solution

Solution
(a) glucose per liter of solution

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SAMPLE PROBLEM 13.2 Solution, cont.

Solution
(b)

(c)

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13.4 Factors That Affect Solubility

Topics
Temperature
Pressure

Learning Objectives
• Recognize the types of solutions according to their degree of saturation
and state of matter.
• Explain the energy changes associated with solution formation.
• Express the concentration of a solution with different units and
interconvert them.
• Describe how major factors affect the solubility.
• Recognize and explain how the concentration of a solute determines
certain physical properties of a solution.
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 13.4 Factors That Affect Solubility
Temperature
 In many cases, the solubility of solid solutes increases with temperature.
 In a few cases solubility decreases with temperature.
 Gases are generally less soluble at higher temperatures.

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 13.4 Factors That Affect Solubility
Pressure
The solubility of a gas in a liquid is proportional to the pressure
of that gas over the solution (Henry’s law).

c = k.P
low P
low c
c is the concentration (M) of dissolved gas.
P is the pressure of the gas over the solution.
k (mol/[Link]) is a is a proportionality
high P constant called the Henry’s law constant.

high c
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 SAMPLE PROBLEM

Calculate the concentration of carbon dioxide in a soft drink that

was bottled under a partial pressure of 5.0 atm CO2 at 25 C

(a) before the bottle is opened and

(b) after the soda has gone “flat” at 25 C.

The Henry’s law constant for in water at this temperature is 3.1

× 10-2 mol/L. Assume that the partial pressure of CO2 in air is
0.0003 atm and that the Henry’s law constant for the soft drink
is the same as that for water.

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 SAMPLE PROBLEM

Setup
At 25 C, the Henry’s law constant for CO2 in water is

Solution
(a) mol/L

(b) mol/L

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13.5 Colligative Properties
Topics
Vapor-Pressure Lowering
Boiling-Point Elevation
Freezing-Point Depression
Osmotic Pressure
Electrolyte Solutions
Learning Objectives
• Recognize the types of solutions according to their degree of saturation
and state of matter.
• Explain the energy changes associated with solution formation.
• Express the concentration of a solution with different units and
interconvert them.
• Describe major factors affecting the solubility.
• Recognize and explain how the concentration of a solute determines
certain physical properties of a solution.
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 13.5 Colligative Properties

Vapor-Pressure Lowering
Colligative properties are properties that depend on the
number of solute particles in solution but do not depend on
the nature of the solute particles.

That is, colligative properties depend on the concentration of

solute particles regardless of whether those particles are
atoms, molecules, or ions.

[Link]

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 13.5 Colligative Properties

Vapor-Pressure Lowering
When a non-volatile solute (one that does not exert a vapor
pressure) is dissolved in a liquid, the vapor pressure exerted
by the liquid decreases.

This relationship is expressed by Raoult’s law,

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 13.5 Colligative Properties

Vapor-Pressure Lowering
In a solution containing only one solute:
X1: solvent fraction

X2: solute fraction

=
P1: vapor pressure of
the solvent over the
solution

P10: vapor pressure of

the pure solvent
Vapor-Pressure Lowering

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 13.5 Colligative Properties

Vapor-Pressure Lowering

The vapor pressure lowering is

due to the reduced entropy
difference between the solution
and the gas phase compared to
that between the pure liquid (i.e.,
pure solvent) and the gas phase

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 13.5 Colligative Properties

Vapor-Pressure Lowering

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 SAMPLE PROBLEM 13.5

Calculate the vapor pressure of water over a solution made

by dissolving 225 g of glucose in 575 g of water at 35C.

Setup
Molar masses of glucose and water are 180.2 and 18.02
g/mol, respectively.

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 SAMPLE PROBLEM 13.5

Solution

The vapor pressure of water over the solution is 40.6 mmHg.

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 13.5 Colligative Properties

Vapor-Pressure Lowering
If both components of a solution are volatile (i.e., have
measurable vapor pressure), the vapor pressure of the
solution is the sum of the individual partial pressures exerted
by the solution components.

Raoult’s law applies in this case (for an ideal solution):

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 13.5 Colligative Properties

Vapor-Pressure Lowering

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 13.5 Colligative Properties
Consider a mixture of benzene and toluene (both volatile):

CH3

benzene toluene

; (

The benzene-toluene solution is an example of an ideal solution,

which is simply a solution that obeys Raoult’s law.
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 13.5 Colligative Properties

Boiling-Point Elevation
The boiling point of a substance is the temperature at which
its vapor pressure equals the external atmospheric pressure.

Because the presence of a nonvolatile solute lowers the vapor

pressure of a solution, it also affects the boiling point of the
solution—relative to that of the pure liquid.

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 13.5 Colligative Properties
Boiling-Point Elevation

0
∆ 𝑇 b =𝑇 b − 𝑇 b

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 13.5 Colligative Properties

Boiling-Point Elevation
The value of is proportional to the concentration, expressed
in molality, of the solute in the solution.

where m is the molality of the solution and is the molal

boiling-point elevation constant.

The units of are °C/m.

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 13.5 Colligative Properties

Boiling-Point Elevation

TABLE 13.2 Molal Boiling-Point Elevation and Freezing-Point Depression

Constants of Several Common Solvents
Solvent Normal Boiling Point () Normal Freezing Point ()

Water 100.0 0.52 0.0 1.86

Benzene 80.1 2.53 5.5 5.12
Ethanol 78.4 1.22 -117.3 1.99
Acetic acid 117.9 2.93 16.6 3.90
Cyclohexane 80.7 2.79 6.6 20.0

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 13.5 Colligative Properties

Boiling-Point Elevation
The boiling point of a 1.00-m aqueous solution of a
nonvolatile, nonelectrolyte:

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 13.5 Colligative Properties

Freezing-Point Depression

0
∆ 𝑇 f =𝑇 −𝑇 f f

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 13.5 Colligative Properties

Freezing-Point Depression

where m is the concentration of solute expressed in molality

and is the molal freezing-point depression constant.

Like , has units of °C/m.

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 SAMPLE PROBLEM 13.6 Setup

Ethylene glycol is a common antifreeze. It is water soluble and

fairly nonvolatile.

Calculate (a) the freezing point and (b) the boiling point of a
solution containing 685 g of ethylene glycol in 2075 g of
water.

Setup
The molar mass of ethylene glycol () is 62.07 g/mol.

and for water are 1.86°C/m and 0.52°C/m, respectively.

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 SAMPLE PROBLEM 13.6 Solution

Solution

(a)
The freezing point of the solution is (0.00  9.89).

The boiling point of the solution is (100.0 + 2.8)102.8

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 13.5 Colligative Properties
Osmotic Pressure
 Osmosis is the selective passage of solvent molecules through a
semi-permeable membrane from a dilute to a more concentrated
solution.
 The solvent molecules are allowed to pass through the membrane
but the solute molecules are not.

more
dilute
concentrated

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13.5 Colligative Properties
Osmotic pressure ():
It is the pressure required to stop osmosis.
 = MRT
where M is the molarity of the solution, R is the gas constant
(0.08206 L · atm/K · mol), and T is the absolute temperature.

Reverse Osmosis

Apply Pressure
Greater Than 
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13.5 Colligative Properties

[Link]
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13.5

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 13.5 Colligative Properties
Electrolyte Solutions
For every mole of CaCl2 dissolved, we get three moles of ions
in solution.
When the solute is an electrolyte, we must consider the
total number of ions present.
moles of particles in solution
van’t Hoff Factor: i =
moles of solute dissolved
NaCl(aq) Na+(aq) + Cl-(aq)

For sodium chloride, the calculated value of i is 2. For

CaCl2 the value is 3.
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 13.5 Colligative Properties

Electrolyte Solutions

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 13.5 Colligative Properties

Electrolyte Solutions
In reality, the measured (experimental) value of is usually
smaller than the calculated (theoretical) , due to the
formation of ion pairs.

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 13.5 Colligative Properties

TABLE 13.3 Calculated and Measured van’t Hoff Factors of 0.0500-M Electrolyte
Solution at 25
Electrolyte i (Calculated/Theoretical) i (Measured)
Sucrose*** 1 1.0
HCl 2 1.9
NaCl 2 1.9
2 1.3
3 2.7
Fe 4 3.4

*** nonelectrolyte

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 SAMPLE PROBLEM 13.7 Setup

The osmotic pressure of a 0.0100 M potassium iodide KI

solution at 25°C is 0.465 atm. Determine the experimental
(measured) van’t Hoff factor for KI at this concentration.

Setup
R = 0.08206 L · atm/K · mol, and T = 298 K.

Solution

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13.6 Calculations Using Colligative Properties

Topics
Calculations Using Colligative Properties

Learning Objectives
• Recognize the types of solutions according to their degree of saturation
and state of matter.
• Explain the energy changes associated with solution formation.
• Express the concentration of a solution with different units and
interconvert them.
• Describe major factors affecting the solubility.
• Recognize and explain how the concentration of a solute determines
certain physical properties of a solution.
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 13.6 Calculations Using Colligative Properties
Calculations Using Colligative Properties
Although any of the four colligative properties can be used to
determine the molar mass of solute, only freezing-point
depression and osmotic pressure are used in practice because
they show the most pronounced (‫)األكثُر ُوضوحًا‬, and therefore the
most easily measured, changes.

From the experimentally-determined freezing-point depression or

osmotic pressure, we can calculate the solution’s molality or
molarity, respectively (see “Chapter 13-Problems” slides).
Knowing the mass of dissolved solute, we can determine its molar
mass.

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 SAMPLE PROBLEM 13.9
Setup
A solution prepared by dissolving 10.0 g of quinine in 50.0 mL of
ethanol has a freezing point 1.55°C below that of pure ethanol.

Determine the molar mass of quinine. (The density of ethanol is

0.789 g/mL.) Assume that quinine is a nonelectrolyte. K f = 1.99

Setup

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 SAMPLE PROBLEM 13.9 Solution

Solution

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 SAMPLE PROBLEM 13.10 Setup

A solution is prepared by dissolving 50.0 g of hemoglobin in

enough water to make 1.00 L of solution. The osmotic pressure of
the solution is measured and found to be 14.3 mmHg at 25°C.

Calculate the molar mass of hemoglobin.

Setup

R = 0.08206 L · atm/K · mol, T = 298 K, and

 = 14.3 mmHg/(760 mmHg/atm) = 1.88 × 10–2 atm.

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 SAMPLE PROBLEM 13.10 Solution

Solution

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