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LOOKING AHEAD
Many of the chemicals you use, both in the laboratory and at
home, are not pure substances; they are aqueous solutions. In this
chapter you will study the dissolving process and some of the
types of solutions that result. You will also learn about the quanti-
tative aspects of solutions, because the properties of solutions
depend not only on their composition, but also on their concen-
tration—the relative proportions of solute and solvent.
When you have completed this chapter, you should be able to:
■ Define solution, solute, solvent, solubility, and saturation.
■ Describe the effects of temperature and pressure on the solubil-
ity of various solutes.
■ Define and use concentration units such as molarity, percent by
mass, and parts per million.
■ Describe the effect of a solute on the vapor pressure, boiling
point, and freezing point of a liquid solvent.
■ Use and interpret solubility curves.
283
What Is a Solution?
A solution is a homogeneous mixture consisting of a solvent and
a solute. The solvent is what does the dissolving. The solute is
what is dissolved. When substances of different phases, such as a
solid and a liquid, are mixed to form a solution, the solvent
retains its phase, while the phase of the solute changes. In a water
solution of salt, for example, the solution is a liquid. Therefore
water, the liquid, is the solvent, while salt, which was originally a
solid, is the solute. When the substances that are mixed to form a
solution start out in the same phase, the substance present in
greater quantity is generally called the solvent. However, the dis-
tinction is not important.
You learned that a homogeneous mixture is uniform in com-
position—it has only one phase. In other words, a homogeneous
mixture is a uniform system. Solutions are uniform systems. They
are therefore considered to be homogeneous. If you compare sam-
ples of equal volume taken from a salt solution, the quantities of
the solvent—water—and the solute—salt—are the same in each
sample. The salt solution is homogeneous.
Solutions contain one distinguishable, or visible, phase. This
means that you see only one phase with the naked eye or even
with the help of a magnifying lens. This is called a visible, or
macroscopic, view of a solution. Such a view might suggest that
only one kind of matter is present in a solution, because all you
see is a single liquid. If you could actually see the particles in a
solution, however, you would find two kinds of matter: solute
and solvent particles (molecules or ions).
Systems that contain more than one distinguishable sub-
stance are called mixtures. Consider a mixture of salt and sugar.
No matter how finely ground the salt and sugar are, you can still
distinguish two substances in the mixture: salt and sugar. You can
distinguish the substances because boundaries separate the parts
that make up the mixture. No boundaries can be detected in a
solution.
Types of Solutions
There are many different types of solutions. The most com-
mon type is solids dissolved in liquids. Other types of solutions
include:
H
O
H H
H
H O H O
O Na+ O H H CI– H H
H O H O
H
H H
O
H
H2 O C6H6
CCI4 H2O
PRACTICE
8.1 When iodine crystals, I2, are added to carbon tetrachlo-
ride, CCl4, they dissolve readily to form a deep purple
solution. When I2 is added to water, it dissolves only
slightly, producing a pale, yellow-brown mixture. If these
two solutions are mixed together in a test tube and shak-
en, the result is shown below.
Colorless
Purple
Expressing Solubility
Sometimes you will see a compound described as “soluble,”
“slightly soluble,” or “insoluble.” Solubility expressed in these
terms is sometimes too vague to be useful. It is preferable to
express how much solute dissolves in a given amount of solvent
at a specific temperature. This information can be determined
experimentally or found in a reference table. In either case, solu-
bility refers to the maximum amount of solute that can be dis-
solved in a given amount of solvent at some specific temperature.
As you will soon learn, this information tells you about solubility
in terms of saturated solutions.
Solubility can be expressed precisely in various ways, depend-
ing on the units that are most convenient to use. Following are
some examples:
grams of solid solute per 100 grams of liquid solvent
grams of gaseous solute per 1000 mL of liquid solvent
milliliters of liquid solute per liter of liquid solvent
molarity or molality (These terms are defined on pages 299
and 304.)
parts per million
120
NaNO3
110
100
Grams of solute/100g H2O
KNO3
90
80
HCI
70
NH4CI
60
KCI
50
40 NaCI
30
20
KCIO3 NH3
10
SO2
0
0 10 20 30 40 50 60 70 80 90 100
Temperature (°C)
Saturated Solutions
If you add sugar to water, at first it dissolves. However, if you
continue to add sugar, the solution eventually becomes saturated,
and will dissolve no more sugar at that temperature. Why does
this happen? A common misconception is that the water has
become full, and has no more room for additional solute. You can
test this idea easily at home. Add a large quantity of sugar to a
PRACTICE
8.4 A single crystal of sodium thiosulfate, Na2S2O3, is added to
a clear solution of that substance. The crystal grows larger,
and then a large number of additional crystals form. A
considerable amount of heat is released during the crystal-
lization process.
(a) Was the original solution saturated, unsaturated or
supersaturated? How do you know?
(b) Is the dissolving of sodium thiosulfate in water
endothermic or exothermic? How do you know?
SAMPLE PROBLEM
PROBLEM
How many grams of KClO3 are needed to saturate 250 g of
water at 48°C?
SOLUTION
Using the chart, you can see that at 48°C, the solubility
of KClO3 in 100 g of water is 20 g. If 20 g of solute saturates
100 g of water, then how much will saturate 250 g? Set up
the proportion:
20 g KClO3 x g KClO3
100 g H2O 250 g H2O
Solving the equation, you see that x 50 g of KClO3.
PRACTICE
8.5 At what temperature will 90 g of NaNO3 exactly saturate
100 g of water?
8.6 A solution is made by adding 60 g of NH4Cl to 100 g of
water at 80°C. Is the solution saturated, unsaturated, or
supersaturated?
8.7 A saturated solution of KClO3 is prepared in 100 g of water
at 70°C. The solution is then cooled to 30°C. How many
grams of KClO3 crystallize out? (The solution does not
become supersaturated.)
8.8 How many grams of NaCl are needed to form a saturated
solution in 25 g of water at 100°C?
8.9 (For experts) A solution was made by adding 80 g of
NaNO3 to 100 g of water at a temperature of 24°C. The
solution was kept in an open container at that tempera-
ture, until crystals began to form.
Temperature
Look at the solubility curves in Figure 8-3 on page 290 again.
Each curve describes the composition of a particular saturated
solution at any specific temperature. For six of the ten solutes
shown (KI, NaNO3, KNO3, NH4Cl, KCl, and KClO3), the curves
rise. This indicates that the solubilities of the solids in water
increase with an increase in temperature. For solid NaCl, the
curve is nearly horizontal. This shows that little change in solu-
bility takes place with increasing temperature. In other words,
NaCl is just as soluble in hot water as it is in cold water. The
curves for the gases NH3, HCl, and SO2 show a decrease in solu-
bility with increasing temperature. This is typical of gases.
The effect of an increase in temperature on a physical or chem-
ical change depends on whether the change is endothermic or
exothermic. An increase in temperature will promote any change
that is endothermic, and will inhibit any change that is exother-
mic. (This concept is more fully discussed in Chapter 10.) The dis-
solving of a solid in a liquid is usually endothermic, because more
energy is absorbed in breaking the bonds within the solid, than is
Pressure
Liquids and solids are virtually incompressible. Thus an
increase in pressure has little effect on the solubility of liquids
and solids.
Gases, on the other hand, can easily be compressed. The solu-
bility of a gas in water at constant temperature is proportional to
the pressure of the gas. More gas will dissolve in water as the pres-
sure of the gas is increased. In the manufacture of carbonated
beverages, for example, the solubility of carbon dioxide in water
is greatly increased by increasing the pressure on the gas.
The effect of pressure on the solubility of gases is demonstrated
every time you open a bottle of carbonated beverage. Before you
open the bottle, you observe that there are no bubbles forming in
the liquid. The dissolved carbon dioxide has reached equilibrium
at high pressure. When you open the bottle, you decrease the pres-
sure, and the carbon dioxide becomes less soluble and begins to
bubble out of the liquid. Eventually, the system will reach equilib-
rium at its new pressure and stop bubbling. The beverage has
become “flat.” By keeping the beverage cold and the bottle sealed,
you are maintaining the conditions which maximize the solubility
of a gas in a liquid—low temperature and high pressure.
PRACTICE
8.10 What is the usual effect of an increase in temperature on
the solubility of solids in liquids?
8.11 What is the usual effect of an increase in temperature on
the solubility of gases in liquids?
8.12 A sealed container holds carbon dioxide gas and water.
What effect would decreasing the volume of the container
Percentage Concentration
The percentage concentration of a solution can be expressed
as the parts by mass of solute per 100 parts by mass of total solu-
tion. A 10-percent salt solution by mass contains 10 grams of salt
dissolved in 90 grams of water—that is, 10 grams of salt in 100
grams of solution.
SAMPLE PROBLEM
PROBLEM
A sample of tap water with a mass of 200. grams is found to
contain 0.040 gram of Ca2 ion.
(a) What is the concentration of Ca2 ion in the solution
in percent by mass?
(b) What is the concentration of Ca2 ion in the solution
in parts per million?
SOLUTION
(a) To find the percent of Ca2 by mass, use the equation
grams of solute
% by mass 100
grams of solution
0.040 gram
% by mass 100 0.020%
200 grams
0.040 gram
ppm 1,000,000 200 ppm
200 grams
PRACTICE
8.14 Find the concentration of solute in each of the following
solutions in parts per million.
(a) 0.0040 gram of sodium chloride in 1000. grams of
solution
(b) 0.035 gram of sodium in 250 grams of soda.
8.15 According to the label, a certain brand of cola soda con-
tains 27 grams of sugar per 250 grams of soda. What is the
percent of sugar, by mass, in that soda?
8.16 The concentration of sodium ions in a certain brand of
mineral water is 40. parts per million. If a bottle of this
water contains 250. grams of the mineral water, what is
the total mass of the sodium ions in the bottle?
Molarity
Chemical reactions result from the collisions of particles.
Chemists therefore often need to know how many particles of
solute are dissolved in a given volume of solution. Calculations
that involve molar concentration, or molarity, are useful in these
situations. A 1-molar (1 M ) solution contains 1 mole (molar
mass) of solute dissolved in 1 liter of solution. Expressed as a for-
mula,
moles of solute moles
molarity or M
liters of solution L
If you know two of the variables in the formula, you can calculate
the third.
SOLUTION
Mass and volume are given; molarity is required. To calculate
molarity according to the formula, you must first convert
grams of solute to moles and milliliters of solution to liters.
2g
moles of solute 0.050 mole
40 g>mole
200. mL
liters of solution 0.200 L
1000. mL>L
0.050 mole
molarity 0.25 M
0.200 L
PROBLEM
2. How many moles of NaOH are contained in 200 mL of
0.25 M NaOH?
SOLUTION
Molarity and volume are given; moles are required. After
converting milliliters to liters, as in Sample Problem 1, you
can solve the molarity formula.
moles
M
L
x mole
0.25 M
0.2 L
x 0.05 mole
PROBLEM
3. How many milliliters of 0.25 M NaOH must be taken
from a stock bottle to obtain 2.0 g of NaOH?
PROBLEM
4. How do you prepare 200 mL of 0.25 M NaOH solution?
SOLUTION
Find the number of moles of solute you need, and then con-
vert to grams.
PROBLEM
5. A chemist is sometimes interested in the molar concen-
tration of a specific ion. For example, what is the con-
centration of Cl in a solution labeled 0.2 M CaCl2?
PRACTICE
8.17 Find the molarity of the following aqueous solutions.
(a) 2.0 moles of HCl in a volume of 500 mL
(b) 20.0 g of NaOH in a volume of 2.0 L
(c) 23 g of C2H5OH in a volume of 500 mL
8.18 How many grams of solute are needed to make each of the
following aqueous solutions?
(a) 4.00 L of 2.00 M HNO3
(b) 200. mL of 4.00 M glucose (Molar mass of glucose
180 g/mole.)
8.19 What is the molarity of sodium ion, Na, in 50.0 mL of a
solution containing 10.6 g of sodium carbonate, Na2CO3?
Dilution Problems
We have used the relationship,
moles moles solute
M , or molarity
L liters of solution
If we are solving for moles, this equation becomes
moles M L, or moles molarity liters.
When we dilute a solution by adding additional solvent, we do
not change the number of moles of solute. Therefore, the molar-
ity liters in the original solution is the same as the molarity
SAMPLE PROBLEMS
PROBLEM
1. How much water must be added to 100 mL of a 0.2 M
solution to obtain a 0.10 M solution?
SOLUTION
In this problem, the original solution is being diluted with
water. You can use the dilution equation in which Mo and Vo
are the original molarity and volume, and Mf and Vf are the
final molarity and volume. Original volume, the original
molarity and final molarity are given; final volume is
required.
Mo Vo Mf Vf
0.2 M 100 mL 0.1 M x mL
x 200 mL
The final volume of the solution must be 200 mL. However,
on careful reading of the question, you find that you are
asked for the amount of water to be added. Since the original
volume was 100 mL, and the final volume is 200 mL, you
need to add 100 mL of water.
PROBLEM
2. If 400 mL of H2O are added to 200 mL of 0.6 M NaOH,
what is the molarity of the new solution?
SOLUTION
Once again, you can use the dilution equation. The original
volume, the original molarity, and the amount of water
PRACTICE
8.20 A chemist has 40. mL of 6.0 M NaOH that he wishes to
dilute to a concentration of 0.50 M. What should be the
final volume of his solution?
8.21 A chemist carefully pours 50. mL of 4.0 M sulfuric acid
into a beaker of water. The total, final volume in the
beaker is 200. mL. What is the new concentration of the
acid?
8.22 A student added 50.0 mL of 2.0 M aqueous HCl to 450 mL
of water. What is the molarity of the new solution?
8.23 (For experts) A chemist mixed 50.0 mL of 2.0 M HCl with
100. mL of 3.0 M HCl, and then added an additional 100.
mL of water. What is the molarity of HCl in the resulting
solution?
Molality
Calculations involving molar concentration, or molarity, are
used when chemists have to know how many particles of solute
are dissolved in a given volume of solution. Sometimes they must
know how many particles of solvent are in a solution, or they need
to know the total number of particles (solute and solvent) in a solu-
tion. In these cases, their calculations involve molal concentration,
or molality.
A 1-molal solution (1 m) contains 1 mole of solute dissolved
in 1000 grams, or 1 kg, of solvent. When the solvent is water,
since 1 kg of water has a volume of 1 liter, the molarities and
SAMPLE PROBLEMS
PROBLEM
1. If 1.80 g of glucose, C6H12O6, are dissolved in 50 g of
H2O, what is the molality of the solution?
SOLUTION
First, find the moles of glucose.
1.80 g
moles of solute 0.010 mole
180 g>mole
50 g
kilograms of solvent 0.05 kg
1000 g>kg
PROBLEM
2. If 0.050 mole of sulfur is dissolved in 100. mL of ben-
zene, C6H6, what is the molality of the solution? The
density of benzene is 0.88 gram/milliliter.
88 g 0.088 kg
Now, use the formula to find the molality.
0.050 mole
molality 0.57 m
0.088 kg
PRACTICE
8.24 Find the molality of a solution that is made up of 34.2 g of
sucrose (C12H22O11) dissolved in 250 g of water.
8.25 If 0.0750 mole of iodine is dissolved in 300. mL of benzene
(density 0.880 g/mL), what is the molality of the solution?
Switch Source of
direct voltage
Graphite Bulb
electrodes
Liquid to
be tested
and the bulb lights. Suppose that the electrodes are surrounded
only by air. Can the air alone act as a conductor between the elec-
trodes? No. The bulb does not light when the switch is closed. Air
is a poor conductor of electricity. Now suppose that a piece of
metal is placed across the electrodes. This time, when the switch
is closed, the bulb glows brightly. The metal is a good conductor
of electricity. Next, place the electrodes in a water solution of an
ionic compound. What happens this time? The bulb lights, just as
it did when the electrodes were connected by a strip of metal. The
brightness of the bulb is a fairly good measure of the number of
charge carriers in the solution. The solution, like the strip of
metal, is a good conductor of electricity.
Compounds that conduct electricity in solution are called
electrolytes. Electrolytes contain mobile, charged particles (ions)
in the solution. Some electrolytes form large numbers of ions in
solution and cause the bulb to glow brightly. Such electrolytes are
called strong electrolytes. Other compounds, such as acetic acid
(CH3COOH) and ammonia (NH3), are poor conductors in solu-
tion and are called weak electrolytes. The bulb just barely lights
in these solutions. Some other compounds, such as sugar and
glycerine, do not conduct electricity in solution. The bulb does
not light at all in these solutions. Such compounds are called
nonelectrolytes.
When an ionic solid dissolves, the ions separate and move
about freely in the solution. (When an ionic solid melts, mobile
Colligative Properties
Properties of solutions, such as vapor pressure, boiling point,
and freezing point, are called colligative, or additive, properties.
Colligative properties depend on the number of particles of
solute in a solution, not on the chemical nature of the particles.
Colligative properties, since they are additive, become more pro-
nounced with increased concentration.
If the concentration of the solution is known, the new freez-
ing point and boiling point of the solution can be calculated
by using certain constants, which are characteristic of each
solvent. These constants are called the molal freezing point
depression constant, and the molal boiling point elevation constant.
For water, the molal freezing point depression constant is
1.86°C/m and the molal boiling point elevation constant is
0.52°C/m. To find the change in boiling or freezing point in an
aqueous solution of a nonelectrolyte, multiply the constant by
the molality.
The freezing point change tf 1.86°C m.
The boiling point change tb 0.52°C m.
SAMPLE PROBLEMS
PROBLEM
1. A student dissolved 1.0 mole of sugar in 250 g of H2O.
At what temperature will this solution boil, and at
what temperature will it freeze?
SOLUTION
To calculate the change in boiling or freezing point we must
first know the molality of the solution.
PROBLEM
2. If 16 g of methanol, CH3OH, are dissolved in 250 g of
H2O, at what temperature will this solution freeze?
SOLUTION
First, calculate the molality of the solution. Since molality is
moles of solute per kilogram of solvent, you will need to
express the quantities of solute and solvent in those units.
The 16 g of CH3OH, which has a molar mass of 32 g, is
16 g
or 0.50 mole.
32 g>mole
The 250 g of water is 0.25 kg of water. The molality of the
solution is
0.50 mole
m or 2.0 m.
0.25 kg
Solutions of Electrolytes
Ionic substances break up into their component ions when
they dissolve. This process is called dissociation. The dissolving of
NaCl, for example, can be represented by the equation
H2O
NaCl (s) h Na (aq) Cl (aq)
The formation of mobile ions causes these solutions to conduct
electricity. One mole of NaCl will produce one mole of sodium
ions and one mole of chloride ions. In dilute solutions, these ions
behave as independent particles in changing the freezing and
boiling points. One mole of NaCl in water thus produces two
moles of particles, since each NaCl breaks into two ions. The boil-
ing and freezing points are changed twice as much as would be
the case for a nonelectrolyte.
To calculate the freezing point of electrolytes, we introduce a
new term to our equation, which becomes
tf 1.86°C m i
The new term, i, is the number of ions produced when the sub-
stance dissociates. For NaCl, i 2. For BaCl2, i 3, since BaCl2
dissociates to produce one Ba2 ion and two Cl ions. For sodium
sulfate, Na2SO4, i 3. Sodium sulfate forms two sodium ions and
one sulfate ion. Note that polyatomic ions, such as the sulfate, do
not break up when dissolved. Boiling point problems are solved
similarly, using the equation
tb 0.52°C m i
SAMPLE PROBLEM
PROBLEM
At what temperature will a 0.20 m solution of CaCl2 freeze?
SOLUTION
CaCl2 is an ionic substance; therefore, it is an electrolyte. To
find the freezing point we need to consider the number of
PRACTICE
8.26 What is the freezing point of a solution containing 5.8 g of
NaCl dissolved in 500 g of water?
8.27 Arrange the following solutions from highest freezing
point to lowest:
(a) 2.0 m BaCl2
(b) 2.0 m NaNO3
(c) 3.0 m C6H12O6
(d) 1.5 m K2SO4
Raoult’s Law
You have already seen that the vapor pressure of the solvent
is decreased as solute dissolves in it. As was the case with freez-
ing and boiling points, the vapor pressure of the solvent can be
found if the concentration of the solution is known.
The vapor pressure of the solvent can be found using the
relationship known as Raoult’s law. This law is based on a sim-
ple assumption. Suppose a nonvolatile solute is added to water
until it comprises one tenth of the total molecules in the solu-
tion. Then nine tenths of the molecules are water. Raoult’s law
assumes that if nine tenths of the molecules are water, then
only nine tenths of the molecules can evaporate, and the vapor
pressure is therefore reduced to nine tenths of the original
vapor pressure. To use Raoult’s law you need a new unit of con-
SAMPLE PROBLEM
PROBLEM
The vapor pressure of water at 25°C is 31.7 kPa. What is the
vapor pressure of a solution containing 36.0 g of glucose,
C6H12O6, in 86.4 g of water at 25°C?
SOLUTION
To use Raoult’s law you must first find the mole fraction of
solvent in the solution. Glucose has a molar mass of 180 g,
so 36.0 g of glucose is
36.0 g
0.20 mole.
180 g>mole
Water has a molar mass of 18 g, so 86.4 g of water is
86.4 g
4.8 moles.
18 g>mole
The total number of moles present is
4.8 moles 0.2 mole 5.0 moles.
PRACTICE
8.28 Find the vapor pressure of water at 100°C in a solution
containing 1.00 mole of a nonvolatile solute dissolved in
1000. g of water.
I
s
0 100
Temperature (°C)
Figure 8-5 Effect of a solute on the vapor pressure, freezing point, and
boiling point of water
Osmosis
Osmosis is the process by which a liquid solvent passes
through a semipermeable membrane. A semipermeable membrane
allows the passage of solvent molecules, but not solute molecules.
The membranes of animal cells are semipermeable; therefore,
osmosis is an important biological process.
Osmosis may be explained on the basis of differences in vapor
pressure. Suppose you have two aqueous solutions of different
concentrations, separated by a semipermeable membrane. The
more concentrated solution has a lower vapor pressure than the
more dilute solution. Therefore water molecules will escape from
the concentrated solution more slowly than they will escape the
dilute solution. Since more water molecules escape from the
dilute solution to the concentrated solution than vice versa, there
is a net movement of water from the dilute solution to the con-
centrated solution. The net movement of solvent molecules in
osmosis is from the region of higher vapor pressure to the region
of lower vapor pressure (see Figure 8-6).
CHAPTER REVIEW
B
C
A
0 100
Temperature (°C)