GENERAL CHEMISTRY

P R I N C I P L E S A N D M O D E R N A P P L I C AT I O N S
ELEVENTH EDITION

PETRUCCI HERRING MADURA BISSONNETTE

Solutions and their

Physical Properties 14
PHILIP DUTTON
UNIVERSITY OF WINDSOR
DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY

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 CONTENTS
Solutions and their
14-1 Types of Solutions: Some
Physical Properties Terminology
14-2 Solution Concentration

14-3 Intermolecular Forces and the

Solution Process
14-4 Solution Formation and
Equilibrium
14-5 Solubilities of Gases

14-6 Vapor Pressures of Solutions

14-7 Osmotic Pressure

14-8 Freezing-Point Depression and
Boiling-Point Elevation of
Nonelectrolyte Solutions
14-9 Solutions of Electrolytes

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14-1 Types of Solution: Some Terminology

Solutions are homogeneous mixtures. It is homogeneous because

its composition and properties are uniform, and it is a mixture
because it contains two or more substances in proportions that
can be varied.
Solvent.
Determines the state of matter in which the solution exists.
Is the largest component.
Solutes
Component dissolved in the solution.
Concentrated solution has a relatively large quantity of dissolved
solute(s), and a dilute solution has only a small quantity.
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Slide 14 - 4 General Chemistry: Chapter 14 Copyright © 2017 Pearson Canada Inc.
 14-2 Solution Concentration.
Mass Percent, Volume Percent,
and Mass/Volume Percent

Mass Percent (m/m)

Volume Percent (v/v)
Mass/Volume percent (m/v)

Isotonic saline is prepared by dissolving

0.9 g of NaCl in 100 mL of water
and is said to be:
0.9% NaCl (mass/volume)

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 Parts per Million, Parts per Billion,
and Parts per Trillion
Very low solute concentrations are expressed as:

ppm: parts per million

(µg/g, mg/L)
ppb: parts per billion
(ng/g, µg/L)
ppt: parts per trillion
(pg/g, ng/L)

note that 1.0 L × 1.0 g/mL = 1000 g

ppm, ppb, and ppt are properly m/m or v/v.

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Mole Fraction and Mole Percent
The mole fraction of component i, designated xi ,is the fraction of
all the molecules in a solution that are of type i.

Amount of component i (in moles)

𝜒i =
Total amount of all components (in moles)

The sum of the mole fractions of all the solution

components is 1. 𝜒 + 𝜒 + 𝜒 + … = 1
i j k

The mole percent of a solution component is the percent of all

the molecules in solution that are of a given type.

Mole % i = 𝜒i×100%

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Molarity

Amount of solute (in moles)

Molarity (c) =
Volume of solution (in liters)

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Molality
A concentration unit that is independent of temperature, and
also proportional to mole fraction in dilute solutions, is
molality (m) the number of moles of solute per kilogram of
solvent (not of solution).

Amount of solute (in moles)

Molality (m) =
Mass of solvent (in kilograms)

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 2A. A 16.00% aqueous solution of glycerol, C3H5(OH)3,
by mass, has a density of 1.037 g/mL. What is the mole
fraction of glycerol in this solution? (MC=12.011g/mol,
MH= 1.008 g/mol and MO= 15.999 g/mol)

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 14-3 Intermolecular Forces and the Solution
Process Enthalpy of Solution
Three-step approach to ΔHsoln.
First, solvent molecules must be separated from one another.
Some energy is required to overcome the forces of attraction between solvent
molecules. This step should be an endothermic one: ΔHa > 0.
Second, the solute molecules must be separated from one another. This step will
take energy and should be endothermic: ΔHb > 0
Finally, the separated solvent and solute molecules should be attracted to one
another and energy should be released. This is an exothermic step: ΔHc < 0.
The enthalpy of solution is the sum of the three enthalpy changes,

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 Intermolecular Forces in Mixtures
Magnitude of ΔHa, ΔHb, and ΔHc depends
on intermolecular forces.
1. If the intermolecular forces of
attraction are of the same type and of
equal strength, the solute and solvent
molecules mix randomly. A
homogeneous mixture or solution
results. They are called ideal
solutions.
There is no overall enthalpy change in the
formation of an ideal solution from its
components,
ΔHsoln = 0
FIGURE 14-3
Intermolecular Forces in Mixtures

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2. If forces of attraction between unlike molecules exceed those
between like molecules, a solution also forms. The properties of
such solutions generally cannot be predicted and they are called
nonideal solutions.
heat release (ΔHc) > heat absorbed (ΔHa + ΔHb),
the solution process is exothermic ΔHsoln<0).

3. If forces of attraction between solute and solvent molecules

are somewhat weaker than between molecules of the same
kind, the solution formed is nonideal.
heat release (ΔHc) < heat absorbed (ΔHa + ΔHb),
the solution process is endothermic ΔHsoln>0).

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 4. Finally, if forces of attraction between unlike molecules are
much weaker than those between like molecules, the
components remain segregated in a heterogeneous mixture.
Dissolution does not occur to any significant extent.

From a thermodynamic perspective,

ΔsolnG= ΔsolnH-TΔsolnS,

If ΔsolnG < 0, the solution process is spontaneous,

If ΔsolnG > 0, the solution process is not spontaneous.

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 14-4 Solution Formation and Equilibrium
• When a solid solute and liquid solvent are mixed, only dissolution occurs at first,
then the reverse process of crystallization starts and some dissolved atoms, ions, or
molecules return to the undissolved state.
• When dissolution and crystallization occur at the same rate, the solution is in a
state of dynamic equilibrium. The quantity of dissolved solute remains constant
with time, and the solution is said to be a saturated solution.
• The concentration of the saturated solution is called the solubility of the solute in
the given solvent.
• Solubility varies with temperature, and a solubility temperature graph is called a
solubility curve.

FIGURE 14-9
Formation of a saturated solution

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 14-4 Solution Formation and Equilibrium
• In preparing a solution, if solute is less than that would be
present in the saturated solution, the solution is an
unsaturated solution.
• If the solution is a saturated solution and the temperature is
changed to a value at which the solubility is lower (this
generally means a lower temperature), the excess solute
crystallizes from solution, but occasionally all the solute
may remain in solution.
• If the quantity of solute is greater than in a saturated
solution, the solution is said to be a supersaturated
solution. A supersaturated solution is unstable, and if a few
crystals of solute are added to start crystallization, the
excess solute crystallizes.

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 Solubility as a Function of Temperature
Generally, the solubilities of ionic substances (about 95% of
them) increase with increasing temperature.

Le Châtelier’s principle; heat added to a system at equilibrium

stimulates the heat-absorbing, or endothermic, reaction.

When ΔsolnH>0, raising the temperature stimulates dissolving

and increases the solubility of the solute.

Conversely, if ΔsolnH<0(exothermic), the solubility decreases

with increasing temperature. In this case, crystallization being
endothermic is favored over dissolving.

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 4B. If saturated solution of KClO4 at 40°C is cooled to
20°C, calculate the percent yield for the recrystallization of
KClO4.
(Solubility of KClO4 at 20ºC is 3.0 g and 40ºC is 4.84 g.)

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 14-5 Solubility of Gases
Effect of Temperature

Most gases are less soluble in

water as temperature increases.
In organic solvents the reverse
is often true.

FIGURE 14-12
Effect of temperature on the solubilities of gases

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Effect of Pressure
William Henry found that the solubility of a gas increases with
increasing pressure.

C = k×Pgas (14.2)

C 23.54 mL N2/L
k= = = 23.54 ml N2/L atm
Pgas 1.00 atm

C 100 mL N2/L
PN2 = = = 4.25 atm
k 23.54 ml N2/atm

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 We can rationalize Henry’s law as follows:

• In a saturated solution, the rate of evaporation of gas molecules from

solution and the rate of condensation of gas molecules into the solution
are equal. Both of these rates depend on the number of molecules per
unit volume.

• With increasing pressure on the system, the number of molecules per

unit volume in the gaseous state increases (through an increase in the
gas pressure), and the number of molecules per unit volume must also
increase in the solution (through an increase in concentration).
FIGURE 14-13
Effect of pressure on the solubility of a gas

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 5A. Determine the partial pressure of O2 above an aqueous
solution at 0°C known to contain 5.00 mg O2 per 100.0
mL of solution. The Henry’s law constant for O2 dissolved
in water is k = 2.18 ×10-3 M atm-1 . (MO= 15.999 g/mol)

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 14-6 Vapor Pressures of Solutions
With two components, solvent A and solute B.
Raoult found that a dissolved solute lowers the vapor pressure of the
solvent.
Raoult’s law states that the partial pressure exerted by solvent vapor
above an ideal solution, PA, is the product of the mole fraction of
solvent in the solution, xA, and the vapor pressure of the pure
solvent at the given temperature, PA°.

(14.3)

xA + xB = 1.00, xA must be less than 1.00, and PA must be smaller

than PA°.
Strictly speaking, Raoult’s law applies only to ideal solutions. However, even in
nonideal solutions, the law often works reasonably well for the solvent in dilute
solutions,
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 6A. The vapor pressure of pure hexane and pentane at
25°C are 149.1 mmHg and 508.5 mmHg, respectively. If
a hexane pentane solution has a mole fraction of hexane of
0.750, what are the vapor pressures of hexane and pentane
above the solution? What is the total vapor pressure?

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 7A. What is the composition of the vapor in equilibrium
with the hexane pentane solution described in Example
6A?

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 14-7 Osmotic Pressure
For a solution with a volatile solvent, but
one or more nonvolatile solutes, such as
glucose, sucrose, or urea.
Raoult’s law still applies to the solvent in
such solutions, the vapor pressure of the
solvent is lowered.
The curved arrow indicates that water
vaporizes from A and condenses into B.
The driving force is that the vapor
pressure of H2O above A is greater than
that above B.
When the mole fraction of H2O is the same
in both solutions, the net transfer of H2O Observing the direction of flow
stops. of water vapor

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 14-7 Osmotic Pressure
An aqueous sugar solution in a long glass
tube is separated from pure water by a
semipermeable membrane (permeable to
water only). Water molecules can pass
through the membrane in either direction.
But because the concentration of water
molecules is greater in the pure water
than in the solution, there is a net flow
from the pure water into the solution. This
net flow, called osmosis, causes the
solution to rise in the tube.
The necessary pressure to stop osmotic flow
is called the osmotic pressure of the
solution.

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The magnitude of osmotic pressure depends only on the number of
solute particles per unit volume of solution. It does not depend on
the identity of the solute.
Properties of this sort, whose values depend only on the concentration
of solute particles in solution and not on what the solute is, are
called colligative properties.

Osmotic Pressure, π
For dilute solutions of electrolytes:

πV = nRT

n
π= RT = c×RT (14.4)
V
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 8A. What is the osmotic pressure at 25°C of an aqueous
solution that contains 1.50 g C12H22O11 in 125 mL of
solution? (Molar mass of C12H22O11= 342.3 g/mol)

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 9A. Creatinine is a by-product of nitrogen metabolism and
can be used to provide an indication of renal function. A
4.04 g sample of creatinine is dissolved in enough water to
make 100.0 mL of solution. The osmotic pressure of the
solution is 8.73 mmHg at 298 K. What is the molar mass
of creatinine?

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 14-8 Freezing-Point Depression and Boiling
Point Elevation of Nonelectrolyte
Solutions
The blue curves represent the phase diagram
for a pure solvent.
The red curves represent the curves for
solvent in a solution.
When a nonvolatile solute is disolved in
solvent, the vapor pressure of solvent
decreases.
The normal melting points and boiling points
in a phase diagram are the temperatures at
which a line at P = 1 atm intersects the
fusion and vapor pressure curves,
respectively.
The freezing point of the solvent in solution is ΔTf = -Kf×m
depressed, and the boiling point is ΔTb = Kb×m
elevated.
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 ΔTf = –Kf×m (14.5)

ΔTb = Kb×m (14.6)

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 10A. Vitamin B2 riboflavin, is soluble in water. If 0.833 g
of riboflavin is dissolved in 18.1 g H2O, the resulting
solution has a freezing point of -0.227 °C.
(Kf(H2O)=1.86ºCmol-1kg)
(a) What is the molality of the solution?
(b)What is the molar mass of riboflavin?

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 14-9 Solutions of Electrolytes
For a strong electrolyte such as NaCl, which produces two moles of ions
in solution per mole of solute dissolved, we would expect the effect on
freezing-point depression to be twice as great as for a nonelectrolyte.
We would expect that i=2.
Similarly, for MgCl2 our expectation would be that i=3.
For such solutes as urea, glycerol, and sucrose (all nonelectrolytes), i = 1.
For the weak acid CH3COOH (acetic acid), which is only slightly
ionized in aqueous solution, we expect i to be slightly larger than one
but not nearly equal to two.
π = i ×M×RT

ΔTf = –i×Kf×m

ΔTb = i×Kb×m
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 11. Predict the freezing point of aqueous 0.00145 m MgCl2.
Kf(H2O)=1.86ºCmol-1kg)

ΔTf = –i×Kf×m

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 Example:An ethanol water
solution is prepared by dissolving
10.00 mL of ethanol, CH3CH2OH
(d = 0.789 g/mL), in a sufficient
volume of water to produce 100.0
mL of a solution with a density of
0.982 g/mL. What is the
concentration
of ethanol in this solution
expressed as (a) volume percent;
(b) mass percent; (c) mass/volume
percent; (d) mole fraction; (e) mole
percent; (f) molarity; (g) molality?
(MC=12.011g/mol, MH= 1.008
g/mol and MO= 15.999 g/mol)

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