Chapter 11

Properties of
Solutions
Chapter 11
Table of Contents
11.1 Solution Composition
11.2 The Energies of Solution Formation
11.3 Factors Affecting Solubility
11.4 The Vapor Pressures of Solutions
11.5 Boiling-Point Elevation and Freezing-Point
Depression
11.6 Osmotic Pressure
11.7 Colligative Properties of Electrolyte Solutions
11.8 Colloids
Section 11.1
Solution Composition

Solution
• A mixture of two or more substances that is
identical throughout Salt water is considered a
• Can be physically separated solution. How

• Composed of solutes and solvents can it be

physically separated?

The substance in the smallest The substance in the larger

amount and the one that dissolves in the amount that dissolves the solute

solvent

Iced Tea Mix Water

Iced Tea
(solute) (solvent)
(solution)

Colloids (milk, fog, jello) are considered solutions

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Section 11.1
Solution Composition

How Does a Solution Form?

As a solution forms, the solvent pulls solute
particles apart and surrounds, or solvates, them.

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 Section 11.1
Solution Composition

Various Types of Solutions

State of State of
Example Solution State of Solute Solvent
Air, natural gas Gas Gas Gas

Antifreeze Liquid Liquid Liquid

Brass Solid Solid Solid
Carbonated water (soda) Liquid Gas Liquid
Seawater, sugar solution Liquid Solid Liquid

Hydrogen in platinum Solid Gas Solid

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Section 11.1
Solution Composition

Student, Beware!

Just because a substance disappears when it

comes in contact with a solvent, it doesn’t
mean the substance dissolved. It may have
reacted. Return to TOC
Section 11.1
Solution Composition

Student, Beware!

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

original solute by evaporating the solvent.
• If you can’t get it back, the substance didn’t dissolve, it
reacted. Return to TOC
Section 11.1
Solution Composition

Types of Solutions

• Saturated
– In a saturated
solution, the solvent
holds as much solute
as is possible at that
temperature.
– Dissolved solute is in
dynamic equilibrium
with solid solute
particles.

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 Section 11.1
Solution Composition

Types of Solutions

• Unsaturated
– If a solution is
unsaturated, less
solute than can
dissolve in the
solvent at that
temperature is
dissolved in the
solvent.

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Section 11.1
Solution Composition

Types of Solutions

• Supersaturated
– In supersaturated solutions, the solvent holds
more solute than is normally possible at that
temperature.
– These solutions are unstable; crystallization can
usually be stimulated by adding a “seed crystal” or
scratching the side of the flask.
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Section 11.1
Solution Composition

Ways of
Expressing
Concentrations
of Solutions
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Section 11.1
Solution Composition

Ways of Expressing Concentration

• Concentration expressions are a ratio of the amount of
solute to the amount of solvent or solution.

– The quantity of solute, solvent, or solution can be expressed in volumes

or in molar or mass amounts.

– Thus, there are several ways to express the concentration of a solution.

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Section 11.1
Solution Composition

moles of solute
Molarity (M ) =
liters of solution

mass of solute
Mass (weight) percent =  100%
mass of solution

moles A
Mole fraction (  A ) =
total moles of solution

moles of solute
Molality ( m ) =
kilogram of solvent
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Section 11.1
Solution Composition

Molarity
• The molarity of a solution is the moles of solute in a liter
of solution.

moles of solute
Molarity(M ) 
liters of solution

– For example, 0.20 mol of ethylene glycol dissolved in enough water to give 2.0
L of solution has a molarity of

0.20 mol ethylene glycol

2.0 L solution  0.10 M ethylene glycol
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 Section 11.1
Solution Composition

Mass Percentage of Solute

• The mass percentage of solute is defined as:

mass of solute
Mass percentage of solute   100%
mass of solution

– For example, a 3.5% sodium chloride solution contains 3.5 grams NaCl in
100.0 grams of solution.

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Section 11.1
Solution Composition
Molality
• The molality of a solution is the moles of solute per
kilogram of solvent.

moles of solute
molality ( m ) 
kilograms of solvent
– For example, 0.20 mol of ethylene glycol dissolved in 2.0 x 103 g (= 2.0 kg)
of water has a molality of

0.20 mol ethylene glycol

2.0 kg solvent  0.10 m ethylene glycol
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Section 11.1
Solution Composition

A Problem to Consider
• What is the molality of a solution containing 5.67 g of
glucose, C6H12O6, dissolved in 25.2 g of water?

– First, convert the mass of glucose to moles.

1 mol C6 H12O 6
5.67 g C6 H12O 6   0.0315 mol C6 H12O 6
180.2 g C6 H12O 6

– Then, divide it by the kilograms of solvent (water).

0.0315 mol C6 H12O 6
Molality  -3
 1.25 m C6 H12O 6
25.2  10 kg solvent
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Section 11.1
Solution Composition

Mole Fraction
• The mole fraction of a component “A” (A) in a solution
is defined as the moles of the component substance
divided by the total moles of solution (that is, moles of
solute and solvent).

moles of substance A
A 
total moles of solution

– For example, 1 mol ethylene glycol in 9 mol water gives a mole fraction for
the ethylene glycol of 1/10 = 0.10.
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Section 11.1
Solution Composition

A Problem to Consider
• An aqueous solution is 0.120 m glucose. What are the
mole fractions of each of the components?

– A 0.120 m solution contains 0.120 mol of glucose in 1.00 kg of water. After

converting the 1.00 kg H O into moles, we can calculate the mole fractions.
2

3 1 mol H 2O
1.00  10 g H 2O   55.6 mol H 2O
18.0 g
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Section 11.1
Solution Composition

A Problem to Consider
• An aqueous solution is 0.120 m glucose. What are the
mole fractions of each of the components?

0.120 mol
 glu cos e   0.00215
(0.120  55.6) mol
55.6 mol
 water   0.998
(0.120  55.6) mol

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 Section 11.2
Atomic
The Energies
Massesof Solution Formation
Energy changes in Solution Formation

Step 1: Solute particles separate from each other. This process is endothermic.
Solute (aggregated) + heat → solute (separated) ΔH >0
solute

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 Section 11.2
Atomic
The Energies
Massesof Solution Formation

Step 2: Solvent particles separate from each other. This process is endothermic.
Solvent (aggregated) + heat → solvent (separated) ΔH >0
solvent

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 Section 11.2
Atomic
The Energies
Massesof Solution Formation

Step 3: Solute and solvent particles mix and form a solution. This step is exothermic.

Solute (separated) + solvent (separated) → solution + heat ΔH <0

mix

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 Section 11.2
Atomic
The Energies
Massesof Solution Formation
Heat (enthalpy) of Solution

The enthalpy change associated with formation of solution.

ΔH = ΔH + ΔH + ΔH
soln solute solvent mix

The overall solution process may be either exothermic or endothermic.

Exothermic process: ΔH < 0 because the sum of the endothermic processes
soln

(ΔH + ΔH ) is smaller than the exothermic term (ΔH ).

solute solvent mix

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Section 11.2
Atomic
The Energies
Massesof Solution Formation

Endothermic process: ΔH ˃ 0 because the sum of the endothermic processes

soln

(ΔH + ΔH ) is larger than the exothermic term (ΔH ).

solute solvent mix

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 Section 11.2
Atomic
The Energies
Massesof Solution Formation

Concept Check

Explain why water and oil (a long chain

hydrocarbon) do not mix. In your explanation,
be sure to address how ΔH plays a role.

Endothermic solution process

H < H + H
mix solute solvent

H >0
soln

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Section 11.2
Atomic
The Energies
Massesof Solution Formation

In General
• One factor that favors a process is an increase
in probability of the state when the solute and
solvent are mixed.
• Processes that require large amounts of energy
tend not to occur.
• Overall, remember that “like dissolves like”.

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Section 11.3
The MoleAffecting Solubility
Factors

• Structural Effects:
 Polarity
• Pressure Effects:
 Henry’s law
• Temperature Effects:
 Affecting aqueous solutions

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 Section 11.3
The MoleAffecting Solubility
Factors

Structural Effects:
Let us examine the difference between Vitamin A and Vitamin C

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 Section 11.3
The MoleAffecting Solubility
Factors
Pressure Effects
• Pressure has little effect on the solubility of a solid or a liquid, but
it significantly affects solubility of a gases
• Suppose that a solution is saturated with CO 2 at low pressure.
- This means that the rate at which CO2 enter the solution is equal
to the rate at which CO2 leave the liquid

A Gaseous

Solute

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 Section 11.3
The MoleAffecting Solubility
Factors
Pressure Effects
• Pressure has little effect on the solubility of a solid or a liquid, but
it significantly affects solubility of a gases
• If we increase the pressure of CO2 above the liquid, then the rate
at which CO2 molecules enter the liquid increases, but the rate at
which CO2 molecules leave the liquid does not change.

A Gaseous

Solute

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 Section 11.3
The MoleAffecting Solubility
Factors
Pressure Effects
• Pressure has little effect on the solubility of a solid or a liquid, but
it significantly affects solubility of a gases
• Thus, the number of CO2 molecules in the solution increases
until the two rates are equal again.

A Gaseous

Solute

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 Section 11.3
The MoleAffecting Solubility
Factors
Pressure Effects
• This effect is described by Henry’s law:
C = kP
C = concentration of dissolved gas, k = constant, P =partial
pressure of gas solute above the solution
• Amount of gas dissolved in a solution is directly proportional to
the pressure of the gas above the solution.

A Gaseous

Solute

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 Section 11.3
The MoleAffecting Solubility
Factors
Temperature Effects (for Aqueous Solutions)
• Although the solubility of most solids in water
increases with temperature, the solubilities of
some substances decrease with increasing
temperature.
• Predicting temperature dependence of solubility
is very difficult.
• Solubility of a gas in solvent typically decreases
with increasing temperature.

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 Section 11.3
The MoleAffecting Solubility
Factors
The Solubilities of Several Solids
as a Function of Temperature
For most solid solutes, warm water will
dissolve more solution than cool water.
For any one particular solid solute's
“ Solubility curve”…
A temp.-mass point on the curve
represents a saturated solution.
A temp.-mass point above the curve
describes an excess of solid that will
remain settled to the bottom of the
saturated solution.
A temp.-mass point below the curve
represents an unsaturated solution that
could possibly dissolve a bit more solute.
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 Section 11.3
The MoleAffecting Solubility
Factors
The Solubilities of Several Gases in
Water
Gases are less soluble in warm water than cool
water.
Warm water particles collide with solute gas
particles more quickly, forcing them out of
solution..

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 Section 11.4
The Vapor Pressures of Solutions

• Liquid solutions have significantly different physical properties

that the pure solvent.
 Ex: a small amount of antifreeze is enough to lower the freezing
point of water and raise the boiling point of water.
 Ex: a small amount of salt is used to melt ice on roads and
sidewalks.

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Section 11.4
The Vapor Pressures of Solutions

• In a closed container at
constant temperature
an equilibrium vapor
pressure is
established.
• The picture on the left
indicates that vapor
molecules leave a
solvent to dilute a
solution. Why?

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Section 11.4
The Vapor Pressures of Solutions

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Section 11.4
The Vapor Pressures of Solutions

• The vapor pressure of a liquid is much different in a

solution than it is in a pure liquid.
• The dissolved nonvolatile solute lowers the vapor
pressure of a solvent.
• The solute decreases the number of solvent molecules
per unit volume lowering the tendency for the molecules
to escape into vapor.

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 Section 11.4
The Vapor Pressures of Solutions

• In a solution that is half nonvolatile

solute particles and half solvent, one
would expect a vapor pressure of 1/2
the pure solvent, since only half as
many molecules can escape.
• That is what is exhibited by such a
solution.

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Section 11.4
The Vapor Pressures of Solutions

• Nonvolatile solute lowers the vapor pressure of

a solvent. The new vapor pressure can be
calculated by

• Raoult’s Law: Psoln = solv Psolv



Psoln = observed vapor pressure of


solution

Psolv
solv = mole fraction of solvent
= vapor pressure of pure solvent
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Section 11.4
The Vapor Pressures of Solutions

Raoult’s Law

• From Raoult’s law we see clearly that

the amount of change in the vapor
pressure is dependent on the amount
of the nonvolatile solute added to the
solution (mole fraction) not the quality
of the solute.

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Section 11.4
The Vapor
Raoult’s Pressures of Solutions
Law

• Raoult’s Law is a
linear equation
(y=mx+b)
• A plot of Psoln vs mole
fraction gives a
straight line with a
slope equal to Psolvent.

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Section 11.4
The Vapor Pressures of Solutions

Nonideal Solutions
• Liquid-liquid solutions where both components
are volatile.

• Modified Raoult’s Law:

PTotal =  A PA + BPB

• Nonideal solutions behave ideally as the mole

fractions approach 0 and 1.

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Section 11.4
The Vapor Pressures of Solutions

Vapor Pressure for a Solution of Two Volatile Liquids

PTotal =  A P +  P

A B B


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 Section 11.4
The Vapor Pressures of Solutions
Summary of the Behavior of Various Types of Solutions

Deviation
Interactive Forces Between
T for Solution from
Solute (A) and Solvent (B) Hsoln Example
Formation Raoult’s
Particles
Law

None (ideal Benzene-

A  A, B  B  A  B Zero Zero
solution) toluene

Negative Acetone-
A  A, B  B < A  B Positive Negative
(exothermic) water

Positive Ethanol-
A  A, B  B > A  B Negative Positive
(endothermic) hexane

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Section 11.4
The Vapor Pressures of Solutions

Concept Check

For each of the following solutions, would you

expect it to be relatively ideal (with respect to
Raoult’s Law), show a positive deviation, or
show a negative deviation?
a) Ethyl alcohol (C2H5OH) and water
b) Hexane (C6H14) and octane (C8H18)

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Section 11.5
Boiling-Point Elevation and Freezing-Point Depression

Colligative Properties
 Boiling-point elevation
 Freezing-point depression
 Osmotic pressure

Colligative properties are called so because they

depend only on the number of particles
present in solution, not on the identity of the
solute particles in an ideal solution.

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 Section 11.5
Boiling-Point Elevation and Freezing-Point Depression

Boiling-Point Elevation
• Recall that the boiling point of a substance is the
temperature at which the vapor pressure equals the
atmospheric pressure.

• Note that the vaporization curve for the

solution is lower than that for the pure

solvent.

• Thus, to obtain the same vapor pressure,

the solution must be at a higher

temperature than the pure solvent.

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 Section 11.5
Boiling-Point Elevation and Freezing-Point Depression
The change in the boiling point can be calculated by:

T = T –0 T
b b b
0
T is the boiling point of
b
the pure solvent

T is the boiling point of

b
the solution

0
T >T T > 0
b b b

T = K m
b b

m is the molality of the solution

K is the molal boiling-point
b
elevation constant ( C/m)
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 Section 11.5
Boiling-Point Elevation and Freezing-Point Depression

Freezing-Point Depression

• Note that the melting curve for the solution is farther to the left than that for

the pure solvent.

• Thus, the temperature at which
the solid solution melts is lower
at a given pressure than that for
the solvent.
• This means that, the solute
causes a decrease of the freezing
point.

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Section 11.5
Boiling-Point Elevation and Freezing-Point Depression
0
DT = T – T
f f f
T 0 is the freezing point of
f
the pure solvent

T is the freezing point of

f
the solution

0
T >T DT > 0
f f f

DT = K m
f f

m is the molality of the solution

K is the molal freezing-point

f
depression constant (˚C/m)
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Section 11.5
Boiling-Point Elevation and Freezing-Point Depression

Exercise

How many grams of fructose (C6H12O6) must be dissolved

in 937 g of acetic acid to raise the boiling point by 9.1 °C?
The boiling point constant for acetic acid is 3.08 °C.Kg/mol

• 1) We utilize this formula:

• ΔT = Kb msolute
• 9.1 °C = (3.08 °C kg mol-1) (moles of solute / 0.937 kg)
• 9.1 °C = (3.287 °C mol-1) (moles of solute)
• Moles of solute = 2.7684 mol
• 2) Determine grams of fructose:
• 2.7684 mol × 180.1548 g/mol = 499 g
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 Section 11.6
Osmotic Pressure

• Suppose we separate a solution and a pure solvent by a semipermeable

membrane, which allow solvent, but not solute molecules to pass through.
• Over time, solvent flows from the pure solvent side of the membrane to
the solution side, increasing the volume of the solution.
• This process is called osmosis.
• Since the volume of the solution is increase the conc. of the solute is
decreasing.

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 Section 11.6
Osmotic Pressure

• The flow of the solvent continues until either the conc. of the two side
equal (not possible) or the pressure exerted by downwards by the gravity
equals the osmotic pressure upwards.

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Section 11.6
Osmotic Pressure

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 Section 11.6
Osmotic Pressure

• We can calculate the osmotic pressure Π, in atm.

 = MRT
 = osmotic pressure (atm)
M = molarity of the solution
R = gas law constant
T = temperature (Kelvin)

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Section 11.6
Osmotic Pressure

Exercise

When 33.4 mg of a compound is dissolved in

10.0 mL of water at 25°C, the solution has an
osmotic pressure of 558 torr. Calculate the
molar mass of this compound.

115 g/mol

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Section 11.7
Colligative Properties of Electrolyte Solutions

• Strong electrolytes affect the freezing point

and boiling point more strongly because they
separate into ions (more particles).
• Strong electrolyte vs. glucose
NaCl vs. C6H12O6

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Section 11.7
Colligative Properties of Electrolyte Solutions

van’t Hoff Factor, i

• The relationship between the moles of solute dissolved
and the moles of particles in solution is usually
expressed as:
moles of particles in solution
i =
moles of solute dissolved

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 Section 11.7
Colligative Properties of Electrolyte Solutions
Ion Pairing
• At a given instant a small percentage of the sodium and
chloride ions are paired and thus count as a single particle.

• The expected value for i can be determined

for a salt by noting the number of ions per

formula unit (assuming complete dissociation

and that ion pairing does not occur).

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Section 11.7
Colligative Properties of Electrolyte Solutions

Ion Pairing
• Ion pairing is most important in concentrated
solutions.
• As the solution becomes more dilute, the ions
are farther apart and less ion pairing occurs.
• Ion pairing occurs to some extent in all
electrolyte solutions.
• Ion pairing is most important for highly charged
ions.

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Section 11.7
Colligative Properties of Electrolyte Solutions

Modified Equations

T = imK

 = iMRT

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