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CHAPTER 17
Reaction Kinetics
Chemists can determine the rates
at which chemical reactions occur.
The Thermite Reaction

The Reaction Process SECTION 1
OBJECTIVES
Explain the concept of
B y studying many types of experiments, chemists have found that reaction mechanism.
chemical reactions occur at widely differing rates. For example, in the
presence of air, iron rusts very slowly, whereas the methane in natural Use the collision theory to
gas burns rapidly. The speed of a chemical reaction depends on the interpret chemical reactions.
energy pathway that a reaction follows and the changes that take place
on the molecular level when substances interact. In this chapter, you
will study the factors that affect how fast chemical reactions take place. Define activated complex.
Relate activation energy

to enthalpy of reaction.
Reaction Mechanisms
If you mix aqueous solutions of HCl and NaOH, an extremely rapid
neutralization reaction occurs, as shown in Figure 1.
H3O+(aq) + Cl−(aq) + Na+(aq) + OH−(aq) ⎯→ 2H2O(l) + Na+(aq) + Cl−(aq)
The reaction is practically instantaneous; the rate is limited only by the
speed with which the H3O+ and OH− ions can diffuse through the water
to meet each other. On the other hand, reactions between ions of the
same charge and between molecular substances are not instantaneous.
Negative ions repel each other, as do positive ions. The electron clouds
of molecules also repel each other strongly at very short distances.
Therefore, only ions or molecules with very high kinetic energy can
overcome repulsive forces and get close enough to react. In this section,
we will limit our discussion to reactions between molecules.
Colorless hydrogen gas consists of pairs of hydrogen atoms bonded
together as diatomic molecules, H2. Violet-colored iodine vapor is also
diatomic, consisting of pairs of iodine atoms bonded together as I2 mol-
ecules. A chemical reaction between these two gases at elevated tem-
peratures produces hydrogen iodide, HI, a colorless gas. Hydrogen
iodide molecules, in turn, tend to decompose and re-form hydrogen
and iodine molecules, producing the violet gas shown in Figure 2. The
following chemical equations describe these two reactions.
H2(g) + I2(g) ⎯→ 2HI(g)
2HI(g) ⎯→ H2(g) + I2(g)

Such equations indicate only which molecular species disappear as a FIGURE 1 As NaOH solution is
poured into HCl solution, a very
result of the reactions and which species are produced. They do not
rapid neutralization reaction occurs.
show the reaction mechanism, the step-by-step sequence of reactions by Excess NaOH turns the phenolph-
which the overall chemical change occurs. thalein indicator pink.
REACTION KINETICS 561

Although only the net chemical change is directly observable for
most chemical reactions, experiments can often be designed that sug-
gest the probable sequence of steps in a reaction mechanism. Each reac-
tion step is usually a simple process. The equation for each step
represents the actual atoms, ions, or molecules that participate in that
step. Even a reaction that appears from its balanced equation to be a
simple process may actually be the result of several simple steps.
For many years, the formation of hydrogen iodide, as shown in Figure
2, was considered a simple one-step process. It was thought to involve the
interaction of two molecules, H2 and I2, in the forward reaction and two
HI molecules in the reverse reaction. Experiments eventually showed,
however, that a direct reaction between H2 and I2 does not take place.
Alternative mechanisms for the reaction were proposed based on
the experimental results. The steps in each reaction mechanism had to
add together to give the overall equation. Note that two of the species
in the mechanism steps—I and H2I—do not appear in the net equation.
FIGURE 2 Colorless hydrogen Species that appear in some steps but not in the net equation are known
iodide gas, HI, decomposes into col- as intermediates. (Notice that they cancel each other out in the follow-
orless hydrogen gas and violet ing mechanisms.) The first possible mechanism has the following two-
iodine gas. Some of the hydrogen gas step pathway.
and iodine gas will reform HI.
Step 1: ⎯→ 2I
I2 ←⎯
Step 2: ⎯→ 2HI
2I + H2 ←⎯
⎯→ 2HI
I2 + H2 ←⎯
The second possible mechanism has a three-step pathway.
Step 1: ⎯→ 2I
I2 ←⎯
Step 2: ⎯→ H I
I + H2 ←⎯ 2
Step 3: ⎯→ 2HI
H2I + I ←⎯
⎯→ 2HI
I2 + H2 ←⎯
The reaction between hydrogen gas and iodine vapor to produce hydro-
gen iodide gas is an example of a homogeneous reaction, a reaction
whose reactants and products exist in a single phase—in this case, the gas
phase.This reaction system is also an example of a homogeneous chemi-
cal system because all reactants and products in all intermediate steps
are in the same phase.
Collision Theory
In order for reactions to occur between substances, their particles (mol-
ecules, atoms, or ions) must collide. Furthermore, these collisions must
result in interactions. The set of assumptions regarding collisions and
reactions is known as collision theory. Chemists use this theory to inter-
pret many of their observations about chemical reactions.
562 CHAPTER 17
AB AB AB AB AB AB
B B
AB AB AB AB
A2
(a) Effective collision, (b) Collision (c) Collision that has

favorable orientation and energy too gentle poor orientation
FIGURE 3 Three possible colli-

Consider what might happen on a molecular scale in one step of a sion patterns for AB molecules are
homogeneous reaction system. We will analyze a proposed first step in shown. Not every collision produces
a hypothetical decomposition reaction. a chemical reaction.
⎯→ A + 2B
AB + AB ←⎯ 2
According to the collision theory, the two AB molecules must collide in

order to react. Furthermore, they must collide with a favorable orienta-
tion and with enough energy to merge the valence electrons and disrupt
the bonds of the AB molecules. If they do so, a reshuffling of bonds
leads to the formation of the products, one A2 molecule and two B
atoms. An effective collision is modeled in Figure 3a.
If a collision is too gentle, the two molecules simply rebound from each
other unchanged. This effect is illustrated in Figure 3b. Similarly, a col-
lision in which the reactant molecules have an unfavorable orientation
has little effect. The colliding molecules rebound without reacting. A
collision that has poor orientation is shown in Figure 3c.
A chemical reaction produces new bonds which are formed between
specific atoms in the colliding molecules. Unless the collision brings the
correct atoms close together and in the proper orientation, the molecules
will not react. For example, if a chlorine molecule collides with the oxygen
end of a nitrogen monoxide molecule, the following reaction may occur.
NO(g) + Cl2(g) ⎯→ NOCl(g) + Cl(g)
This reaction will not occur if the chlorine molecule strikes the nitro-
gen end of the molecule.
Thus, collision theory provides two reasons why a collision between
reactant molecules may fail to produce a new chemical species: the col-
lision is not energetic enough to supply the required energy, or the col-
liding molecules are not oriented in a way that enables them to react
with each other.

Activation Energy
Consider the reaction for the formation of water from the diatomic
gases oxygen and hydrogen according to the following equation.
2H2(g) + O2(g) ⎯→ 2H2O(l)
The enthalpy of formation is quite high: ΔH 0f = −285.8 kJ/mol at
298.15 K. The free-energy change is also large: ΔG 0 = −237.1 kJ/mol.
Why, then, don’t oxygen and hydrogen combine spontaneously and
immediately to form water when they are mixed at room temperature?
Hydrogen and oxygen gases exist as diatomic molecules. When the
molecules approach each other, the electron clouds repel each other, so
the molecules might not meet. For a reaction to occur, the colliding mol-
ecules must have enough kinetic energy to intermingle the valence elec-
trons. In other words, the bonds of these molecular species must be
broken in order for new bonds to be formed between oxygen and hydro-
gen atoms. Bond breaking is an endothermic process, and bond forming
is exothermic. Even though the net process for forming water is exother-
mic, an initial input of energy is needed to overcome the repulsion forces
that occur between reactant molecules when they are brought very close
together. This initial energy input activates the reaction.
Once an exothermic reaction is started, the energy released is
enough to sustain the reaction by activating other molecules. Thus, the
reaction rate keeps increasing. It is limited only by the time required for
reactant particles to acquire the energy and make
contact. Energy from an outside source may start
Reaction Pathways for Forward exothermic reactants along the pathway of reac-
and Reverse Reactions tion. A generalized reaction pathway for an
exothermic reaction is shown as the forward reac-
Activated complex tion in Figure 4. The minimum amount of energy
needed to activate this reaction is the activation
energy represented by Ea . Activation energy is the
Ea
minimum energy required to transform the reactants
into an activated complex.
Reactants Ea′
The reverse reaction, decomposition of water
Energy
Products molecules, is endothermic because the water mole-

ΔE
cules lie at an energy level lower than that of the
Forward Reverse hydrogen and oxygen molecules. The water mole-
reaction reaction cules require a larger activation energy before they
(exothermic) (endothermic) can decompose to re-form oxygen and hydrogen.
The energy needed to activate an endothermic
Course of reaction reaction is greater than that required for the origi-
nal exothermic change and is represented by Ea′ in
FIGURE 4 The difference between the activation energies Figure 4. The difference between Ea′ and Ea is
for the reverse and forward reactions of a reversible reaction
equal to the energy change in the reaction, ΔE. This
equals the energy change in the reaction, ΔE. The quantity for
energy change has the same numerical value for the
ΔE is the same for both directions, but is negative for the
exothermic direction and positive for the endothermic forward reaction as it has for the reverse reaction
direction. but with the opposite sign.
564 CHAPTER 17
The Activated Complex
When molecules collide, some of their high kinetic energy is converted
into internal potential energy within the colliding molecules. If enough
energy is converted, molecules with suitable orientation become acti-
vated. New bonds can then form. In this brief interval of bond breakage
and bond formation, the collision complex is in a transition state. Some
partial bonding exists in this transitional structure. A transitional struc-
ture that results from an effective collision and that persists while old
bonds are breaking and new bonds are forming is called an activated
complex.
Figure 5 graphically breaks down the reaction pathway of the for-
mation of hydrogen iodide gas into three steps. Beginning with the reac-
tants, H2 and I2, a certain amount of activation energy, Ea1, is needed to
form the activated complex that leads to the formation of the interme-
diates H2 and 2I. Then more activation energy, Ea2, is needed to form
the activated complex leading to the intermediates H2I and I. In order
to arrive at the final product, 2HI, another increase in activation energy
is necessary, as seen by the highest peak labeled Ea3.
An activated complex is formed when an effective collision raises the
internal energies of the reactants to their minimum level for reaction, as
in Figure 4. Both forward and reverse reactions go through the same acti-
vated complex. A bond that is broken in the activated complex for the
forward reaction must be re-formed in the activated complex for the
reverse reaction. Observe that an activated complex occurs at a high-
energy position along the reaction pathway.
The kinetic-molecular theory states that the speeds and therefore the
kinetic energies of the molecules increase as the
temperature increases. An increase in speed causes
more collisions, which can cause an increase in the Activation Energy Peaks
number of reactions. However, an increase in the in the Formation of Activated Complexes
reaction rate depends on more than simply the num-
*
ber of collisions, as Figure 3 illustrates.The collisions
between molecules must possess sufficient energy to
form an activated complex or a reaction will not Ea3
take place. Raising the temperature of a reaction
provides more molecules that have this activation *
energy and causes an increase in the reaction rate. * Ea2
Energy
In its brief existence, the activated complex

H2
has partial bonding that is characteristic of both H2I
Ea1+ 2I + I
reactant and product. It may then re-form the
original bonds and separate back into the reac-
H 2 + I2 ΔE
tant particles, or it may form new bonds and sep-
2HI
arate into product particles. The activated
complex, unlike the relatively stable intermediate Course of reaction
products, is a very short-lived molecular complex
FIGURE 5 This energy profile graphically shows the forma-
in which bonds are in the process of being broken tion of three activated complexes (*) during the gas-phase
and formed. reaction H2 + I2 ⎯→ 2HI.

SAMPLE PROBLEM A For more help, go to the Math Tutor at the end of this chapter.
Copy the energy diagram below, and label the reactants, products, E, Ea , and Ea′. Determine the value
of Eforward , Ereverse , Ea , and Ea′.
80
Energy (kJ/mol)
50
Forward Reverse
SOLUTION The energy level of reactants is always at the left-hand end of such a curve, and the energy
level of products is always at the right-hand end. The energy change in the reaction, ΔE, is the
difference between these two energy levels. The activation energy differs in the forward and
reverse directions. It is the minimum energy needed to achieve effective reaction in either
direction. As Ea, it is the difference between the reactant energy level and the peak in the
curve. As Ea′, it is the difference between the product energy level and the peak in the curve.
80
Ea′
Energy (kJ/mol)
50
Products
Ea
ΔE
0
Reactants
Forward Reverse
ΔEforward = energy of products − energy of reactants

ΔEforward = 50 kJ/mol − 0 kJ/mol = +50 kJ/mol
ΔEreverse = energy of reactants − energy of products

ΔEreverse = 0 kJ/mol − 50 kJ/mol = − 50 kJ/mol
Ea = energy of activated complex − energy of reactants

Ea = 80 kJ/mol − 0 kJ/mol = 80 kJ/mol
Ea′ = energy of activated complex − energy of products

Ea′ = 80 kJ/mol − 50 kJ/mol = 30 kJ/mol
566 CHAPTER 17
PRACTICE Answers in Appendix E
1. a. Use the method shown in the sample problem to redraw and

label the following energy diagram. Determine the value of
ΔEforward, ΔEreverse, Ea, and Ea′.
b. Is the forward reaction shown in the diagram exothermic or
endothermic? Explain your answer.
100
Energy (kJ/mol) 50
0
−50
−100
−150
Forward Reverse
2. a. Draw and label an energy diagram similar to the one shown in

the sample problem for a reaction in which Ea = 125 kJ/mol and
Ea′ = 86 kJ/mol. Place the reactants at energy level zero.
b. Calculate the values of ΔEforward and ΔEreverse.
c. Is this reaction endothermic or exothermic? Explain your
answer.
3. a. Draw and label an energy diagram for a reaction in which
Go to go.hrw.com for
Ea = 154 kJ/mol and ΔE = 136 kJ/mol.
more practice problems
b. Calculate the activation energy, Ea′, for the reverse reaction. that ask you to
determine Ea and ΔE.
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SECTION REVIEW 6. What is the difference between an activated com-

1. What is meant by reaction mechanism? plex and an intermediate?
2. What factors determine whether a molecular colli- 7. Explain why, even though a collision may have
sion produces a reaction? energy in excess of the activation energy, reaction
may not occur.
3. What is activation energy?
4. What is an activated complex? Critical Thinking
5. How is activation energy related to the energy 8. ANALYZING INFORMATION Which corresponds to
of reaction? the faster rate: a mechanism with a small activa-
tion energy or one with a large activation energy?
Explain your answer.

SECTION 2
Reaction Rate
OBJECTIVES
Define chemical kinetics, and
explain the two conditions T he change in concentration of reactants per unit time as a reaction
necessary for chemical proceeds is called the reaction rate. The study of reaction rates is con-
reactions to occur. cerned with the factors that affect the rate and with the mathematical
expressions that reveal the specific dependencies of the rate on concen-
Discuss the factors that influ- tration. The area of chemistry that is concerned with reaction rates and
ence reaction rate. reaction mechanisms is called chemical kinetics.
Define catalyst, and discuss

two different types.
Rate-Influencing Factors
Relate the order of a reaction For reactions other than simple decompositions to occur, particles must
to the rate law for the come into contact in a favorable orientation and with enough energy for
reaction. activation. Thus, the rate of a reaction depends on the collision fre-
quency of the reactants and on the collision efficiency. Any change in
Explain and write rate laws reaction conditions that affects the collision frequency, the collision effi-
for chemical reactions. ciency, or the collision energy affects the reaction rate. At least five
important factors influence the rate of a chemical reaction.
Nature of Reactants
Substances vary greatly in their tendencies to react. For example, hydro-
gen combines vigorously with chlorine under certain conditions. Under
the same conditions, it may react only weakly with nitrogen. Sodium
and oxygen combine much more rapidly than iron and oxygen under
similar conditions. Bonds are broken and other bonds are formed in
reactions. The rate of reaction depends on the particular reactants and
bonds involved.
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Topic: Factors Affecting Surface Area
Reaction Rates
Code: HC60564
Gaseous mixtures and dissolved particles can mix and collide freely;
therefore, reactions involving them can occur rapidly. In heterogeneous
reactions, the reaction rate depends on the area of contact of the reac-
tion substances. Heterogeneous reactions involve reactants in two dif-
ferent phases. These reactions can occur only when the two phases are
in contact. Thus, the surface area of a solid reactant is an important fac-
tor in determining rate. An increase in surface area increases the rate of
heterogeneous reactions.
Solid zinc reacts with aqueous hydrochloric acid to produce zinc
chloride and hydrogen gas according to the following equation.
Zn(s) + 2HCl(aq) ⎯→ ZnCl2(aq) + H2(g)
568 CHAPTER 17
This reaction occurs at the surface of the zinc solid. A cube of zinc mea-
suring 1 cm on each edge presents only 6 cm2 of contact area. The same
amount of zinc in the form of a fine powder might provide a contact
area thousands of times greater than the original area. Consequently,
the reaction rate of the powdered solid is much faster.
A lump of coal burns slowly when kindled in air. The rate of burning
can be increased by breaking the lump into smaller pieces, exposing
more surface area. If the piece of coal is powdered and then ignited
while suspended in air, it burns explosively. This is the cause of some
explosions in coal mines.
Temperature
An increase in temperature increases the average kinetic energy of the
particles in a substance; this can result in a greater number of effective
collisions when the substance is allowed to react with another sub-
(a)
stance. If the number of effective collisions increases, the reaction rate
will increase.
To be effective, the energy of the collisions must be equal to or
greater than the activation energy. At higher temperatures, more parti-
cles possess enough energy to form the activated complex when colli-
sions occur. Thus, a rise in temperature produces an increase in collision
energy as well as in collision frequency.
Decreasing the temperature of a reaction system has the opposite
effect. The average kinetic energy of the particles decreases, so they col-
lide less frequently and with less energy, producing fewer effective col-
lisions. Beginning near room temperature, the reaction rates of many
common reactions roughly double with each 10 K (10°C) rise in tem-
perature. This rule of thumb should be used with caution, however. The
actual rate increase with a given rise in temperature must be deter-
mined experimentally.
Concentration (b)
Pure oxygen has five times the concentration of oxygen molecules that
FIGURE 6 Carbon burns faster in
air has at the same pressure; consequently, a substance that oxidizes in
pure oxygen (a) than in air (b)
air oxidizes more vigorously in pure oxygen. For example, in Figure 6, because the concentration of the
the light produced when the lump of charcoal is burned in pure oxygen reacting species, O2, is greater.
is much more intense than the light produced when the charcoal lump
is heated in air until combustion begins. The oxidation of charcoal is a
heterogeneous reaction system in which one reactant is a gas. The reac-
tion rate depends not only on the amount of exposed charcoal surface
but also on the concentration of the reacting species, O2.
In homogeneous reaction systems, reaction rates depend on the con-
centration of the reactants. Predicting the mathematical relationship
between rate and concentration is difficult because most chemical reac-
tions occur in a series of steps, and only one of these steps determines
the reaction rate. If the number of effective collisions increases, the rate

(a) (b) (c) (d)
FIGURE 7 The number of mole-

cules of reacting species affects the
number of possible collisions and increases as well. In general, an increase in rate is expected if the con-
therefore the reaction rate. centration of one or more of the reactants is increased, as depicted by
the model in Figure 7. In the system with only two molecules, shown in
Figure 7a, only one collision can possibly occur. When there are four
molecules in the system, as in Figure 7b, there can be four possible col-
lisions. Under constant conditions, as the number of molecules in the
system increases, so does the total number of possible collisions
between them. Figure 7c and d show a five- and eight-molecule system,
allowing six and sixteen possible collisions, respectively. Lowering the
concentration should have the opposite effect. The actual effect of con-
centration changes on reaction rate, however, must be determined
experimentally.
Presence of Catalysts
Some chemical reactions proceed quite slowly. Sometimes their reac-
tion rates can be increased dramatically by the presence of a catalyst. A
catalyst is a substance that changes the rate of a chemical reaction with-
out itself being permanently consumed. The action of a catalyst is called
catalysis. The catalysis of the decomposition reaction of hydrogen per-
oxide by manganese dioxide is shown in Figure 8. A catalyst provides an
alternative energy pathway or reaction mechanism in which the
potential-energy barrier between reactants and products is lowered.
The catalyst may be effective in forming an alternative activated com-
plex that requires a lower activation energy—as suggested in the ener-
gy profiles of the decomposition of hydrogen peroxide, H2O2, shown in
Figure 9—according to the following equation.
2H2O2(l) ⎯→ O2(g) + 2H2O(l)

FIGURE 8 The reaction rate of
the decomposition of hydrogen per- Catalysts do not appear among the final products of reactions they
oxide, H2O2, can be increased by accelerate. They may participate in one step along a reaction pathway
using a catalyst. The catalyst used and be regenerated in a later step. In large-scale and cost-sensitive reac-
here is manganese dioxide, MnO2, a tion systems, catalysts are recovered and reused. A catalyst that is in the
black solid. A 30% H2O2 solution is same phase as all the reactants and products in a reaction system is called
added dropwise onto the MnO2 in
a homogeneous catalyst. When its phase is different from that of the reac-
the beaker and rapidly decomposes
to O2 and H2O. Both the oxygen and tants, it is called a heterogeneous catalyst. Metals are often used as
water appear as gases because the heterogeneous catalysts. The catalysis of many reactions is promoted by
energy released by the reaction caus- adsorption of reactants on the metal surfaces, which has the effect of
es much of the water to vaporize. increasing the concentration of the reactants.
570 CHAPTER 17
Comparison of Pathways for the Decomposition FIGURE 9 The activation energy
of H2O2 by Various Catalysts for a chemical reaction can be
reduced by adding an appropriate
catalyst.
Ea = 75 Uncatalyzed
Chemically Homogeneous
Ea = 58
catalyzed (I-) processes
Energy (kJ/mol)
Ea = 4 Enzyme
catalyzed
Heterogeneous
process (MnO2)
Course of reaction
Rate Laws for Reactions

Chemistry in Action
The relationship between the rate of a reaction and the concentration Go to go.hrw.com for a full-length
of one reactant is determined experimentally by first keeping the con- article on using spectroscopy to
centrations of other reactants and the temperature of the system con- measure reaction kinetics.
stant. Then the reaction rate is measured for various concentrations of Keyword: HC6RXKX
the reactant in question. A series of such experiments reveals how the
concentration of each reactant affects the reaction rate.
Hydrogen gas reacts with nitrogen monoxide gas at constant volume
and at an elevated constant temperature, according to the following
equation.
2H2(g) + 2NO(g) ⎯→ N2(g) + 2H2O(g)
Four moles of reactant gases produce three moles of product gases;

thus, the pressure of the system diminishes as the reaction proceeds. The
rate of the reaction can, therefore, be determined by measuring the
change of pressure in the vessel with time.
Suppose a series of experiments is conducted using the same initial
concentration of nitrogen monoxide but different initial concentrations
of hydrogen. The initial reaction rate is found to vary directly with the
hydrogen concentration: doubling the concentration of H2 doubles the
rate, and tripling the concentration of H2 triples the rate. If R represents
the reaction rate and [H2] is the concentration of hydrogen in moles per

liter, the mathematical relationship between rate and concentration can
be expressed as follows.
R ∝ [H2]
The ∝ is a symbol that is read “is proportional to.”

Now suppose the same initial concentration of hydrogen is used but
Explosives the initial concentration of nitrogen monoxide is varied.The initial reac-
In a tiny fraction of a second, the reaction rate is found to increase fourfold when the NO concentration is
tions of explosives such as nitroglyc- doubled and ninefold when the concentration of NO is tripled. Thus, the
erin, trinitrotoluene (TNT), and
reaction rate varies directly with the square of the nitrogen monoxide
dynamite are over. These materials are
primarily organic substances containing concentration, as described by the following proportion.
mostly carbon, hydrogen, oxygen, and
nitrogen atoms held together by rela- R ∝ [NO]2
tively weak bonds. When “set off,”
explosive materials experience rapid Because R is proportional to [H2] and to [NO]2, it is proportional to
decomposition. The released elements
their product.
immediately react to form gaseous N2,
CO, CO2, and NO2. The bonds in these
small molecules are much stronger R ∝ [H2][NO]2
than those in the original explosive
material, and so an enormous amount By introduction of an appropriate proportionality constant, k, the
of energy is released. In addition, the
expression becomes an equality.
sudden formation of gaseous material
causes a tremendous increase in pres-
sure that provides the force to demol- R = k[H2][NO]2
ish an unwanted building or break
rocks for building roads. An equation that relates reaction rate and concentrations of reactants is
called the rate law for the reaction. It is applicable for a specific reaction
at a given temperature. A rise in temperature increases the reaction
rates of most reactions. The value of k usually increases as the tempera-
ture increases, but the relationship between reaction rate and concen-
tration almost always remains unchanged.
Using the Rate Law

The general form for the rate law is given by the following equation:
R = k[A]n[B]m
The reaction rate is represented by R, k is the specific rate constant,

and [A] and [B] represent the molar concentrations of reactants. The
respective powers to which the concentrations are raised are represented
by n and m. The rate law is applicable for a specific reaction at a given set
of conditions and must be determined from experimental data.
The power to which a reactant concentration is raised is called the
order in that reactant. The value of n is said to be the order of the reac-
tion with respect to [A], so the reaction is said to be “nth order in A.”
Similarly, for the value of m, the reaction is said to be “mth order in B.”
The orders, or powers, n and m, are usually small integers or zero. An
order of one for a reactant means that the reaction rate is directly pro-
portional to the concentration of that reactant. An order of two means
572 CHAPTER 17
that the reaction rate is directly proportional to the square of the reac-
tant. An order of zero means that the rate does not depend on the con-
centration of the reactant, as long as some of the reactant is present. The
sum of all of the reactant orders is called the order of the reaction, or
overall order. The overall order of the reaction is equal to the sum of the
reactant orders, or n + m. Some examples of observed rate laws that
have been derived experimentally are shown below. Some of these reac-
tions involve nitrogen oxides, which are highly reactive gases that con-
tribute to the formation of smog that can blanket an entire city, as
shown in Figure 10.
3NO(g) ⎯→ N2O(g) + NO2(g) R = k[NO]2

second order in NO,
second order overall
NO2(g) + CO(g) ⎯→ NO(g) + CO2(g) R = k[NO2]2

second order in NO2,
zero order in CO,
2NO2(g) ⎯→ 2NO(g) + O2(g) R = k[NO2]2

second order in NO2,
2H2O2(aq) ⎯→ 2H2O(l) + O2(g) R = k[H2O2]

first order in H2O2,
first order overall
It is important to understand that the orders in the rate law may or may
not match the coefficients in the balanced equation. These orders must
be determined from experimental data.
Specific Rate Constant

The specific rate constant (k) is the proportionality constant relating the
rate of the reaction to the concentrations of reactants. It is important to
remember the following about the value of k:
1. Once the reaction orders (powers) are known, the value of k must be
determined from experimental data.
2. The value of k is for a specific reaction; k has a different value for
other reactions, even at the same conditions.
3. The units of k depend on the overall order of the reaction. FIGURE 10 A cloud of polluted
4. The value of k does not change for different concentrations of reac- air, commonly known as smog, set-
tles over a city. Smog is common in
tants or products. So, the value of k for a reaction remains the same
industrialized areas, where highly
throughout the reaction and does not change with time. reactive gases and particulate matter
5. The value of k is for the reaction at a specific temperature; if we are released into the air.
increase the temperature of the reaction, the value of k increases.
6. The value of k changes (becomes larger) if a catalyst is present.

SAMPLE PROBLEM B For more help, go to the Math Tutor at the end of this chapter.
Three experiments that have identical conditions were performed to measure the initial rate of
the reaction
2HI(g) ⎯→ H2(g) + I2(g)
The results for the three experiments in which only the HI concentration was varied are as follows:
Experiment [HI] (M) Rate (M/s)

1 0.015 1.1 × 10−3
2 0.030 4.4 × 10−3
3 0.045 9.9 × 10−3
Write the rate law for the reaction. Find the value and units of the specific rate constant.
SOLUTION
1 ANALYZE The general rate law for this reaction has the form R = k[HI]n. We need to deduce the value
of the power n.
[HI]
2 PLAN Find the ratio of the reactant concentrations between two experiments, such as 1 and 2, ⎯ ⎯2.
[HI]1
R2
Then, see how the ratio of concentration affects the ratio of rates, ⎯R⎯.
1
[HI] 0.030 M R 4.4 × 10−3 M/s

3 COMPUTE Concentration ratio: ⎯2 = ⎯ = 2.0; rate ratio: ⎯2 = ⎯⎯ = 4.0
[HI]1 0.015 M R1 1.1 × 10−3 M/s
Thus, when the concentration changes by a factor of 2, the rate changes by a factor of 4, or
22, so the rate law is R = k[HI]2.
To find the value of k, we can rearrange the rate law and substitute known values for any
one experiment. Do the following for Experiment 1:
R 1.1 × 10−3 M/s
k = ⎯2 = ⎯⎯ = 4.9 M−1s−1
[HI] (0.015 M)2
4 EVALUATE By comparing items 1 and 3 in the table, we see that when [HI] is tripled, the rate changes
by a factor of 9, or 32. This rate change confirms that the order is 2. The same value of k can
be calculated from any other experiment. Thus, the rate law and k are correct.
1. For the reaction 3A ⎯→ C, the initial concentration of A was 0.2

M and the reaction rate was 1.0 M/s. When [A] was doubled, the
reaction rate increased to 4.0 M/s. Determine the rate law for the
reaction.
2. The rate law for a reaction is found to be rate = k[X]3. By what more practice problems
factor does the rate increase if [X] is tripled? that ask you to
determine rate law and
rate constant.
Keyword: HC6RXKX
574 CHAPTER 17
SAMPLE PROBLEM C For more help, go to the Math Tutor at the end of this chapter.
Three experiments were performed to measure the initial rate of the reaction
A + B ⎯→ C
Conditions were identical in the three experiments, except that the concentrations of reactants varied. The
results are as follows:
Experiment [A] (M) [B] (M) Rate (M/s)

1 1.2 2.4 8.0 × 10−8
2 1.2 1.2 4.0 × 10−8
3 3.6 2.4 7.2 × 10−7
Write the rate law for the reaction. Find the value and units of the specific rate constant.
SOLUTION
1 ANALYZE The general rate law for this reaction has the form R = k[A]n[B]m. We need to calculate the
values of the powers n and m.
2 PLAN Find the ratio of the reactant concentrations between two experiments that have the same
R
[A] but different [B]. Then, see how this ratio affects the ratio of rates, ⎯R⎯2; this ratio of rates
1
lets us find the value of m. A similar approach of comparing two experiments that have the
same [B] but a different [A] lets us find the value of n.
3 COMPUTE First compare Experiments 1 and 2, which have the same [A], to find m:
[B] 2.4 M R 8.0 × 10−8 M/s
Concentration ratio: ⎯1 = ⎯ = 2.0; rate ratio: ⎯1 = ⎯⎯ = 2.0
[B]2 1.2 M R2 4.0 × 10−8 M/s
Thus, when the concentration of B changes by a factor of 2, the rate changes by a factor of
2, or 21. So, m is 1, and the reaction is first order in B.
Then, compare Experiments 1 and 3, which have the same [B], to find n:
[A] 3.6 M R 7.2 × 10−7 M/s
Concentration ratio: ⎯3 = ⎯ = 3.0; rate ratio: ⎯3 = ⎯⎯ = 9.0
[A]1 1.2 M R1 8.0 × 10−8 M/s
Thus, when the concentration of A changes by a factor of 3, the rate changes by a factor of
9, or 32. So, n is 2, and the reaction is second order in A.
The rate law is R k[A]2[B].
To find the value of k, we can rearrange the rate law and substitute known values for any
one experiment. Do the following for Experiment 1:
R 8.0 × 10−8M/s
k= ⎯ = ⎯⎯ = 2.3 × 10−8 M−2s−1
[A]2[B] (1.2 M)2(2.4 M)
4 EVALUATE The same value of k can be calculated from the data for any other experiment. So, the rate
law and the calculation of k are correct.

Rate Laws and Reaction Pathway
The form of the rate law depends on the reaction mechanism. For a
reaction that occurs in a single step, the reaction rate of that step is
proportional to the product of the reactant concentrations, each of
which is raised to its stoichiometric coefficient. For example, suppose
one molecule of gas A collides with one molecule of gas B to form two
molecules of substance C, according to the following equation.
A + B ⎯→ 2C
One particle of each reactant is involved in each collision. Thus, dou-
bling the concentration of either reactant will double the collision fre-
quency. It will also double the reaction rate for this step. Therefore, the
rate for this step is directly proportional to the concentration of A and
B. The rate law for this one-step forward reaction follows.
Rforward = kforward[A][B]
Now suppose the reaction is reversible. In the reverse step, two mol-
ecules of C must decompose to form one molecule of A and one of B or
2C ⎯→ A + B.
Thus, the reaction rate for this reverse step is directly proportional to
[C] × [C]. The rate law for the reverse step is Rreverse = kreverse[C]2.
The power to which the molar concentration of each reactant is raised
in the rate laws above corresponds to the coefficient for the reactant in
the balanced chemical equation. Such a relationship holds only if the
reaction follows a simple one-step path, that is, if the reaction occurs at
the molecular level exactly as written in the chemical equation.
If a chemical reaction proceeds in a sequence of steps, the rate law is
determined from the slowest step because it has the lowest rate. This
slowest-rate step is called the rate-determining step for the chemical
reaction.
Consider the reaction of nitrogen dioxide and carbon monoxide.
NO2(g) + CO(g) ⎯→ NO(g) + CO2(g)
FIGURE 11 This diagram is a
representation of Step 1 in the reac- The reaction is believed to be a two-step process represented by the fol-
tion of nitrogen dioxide and carbon lowing mechanism.
monoxide. Notice the formation of
the intermediate species NO3 after Step 1: NO2 + NO2 ⎯→ NO3 + NO slow
two molecules of NO2 collide. Step 2: NO3 + CO ⎯→ NO2 + CO2 fast
In the first step, shown in Figure 11, two molecules of NO2
collide, forming the intermediate species NO3. This molecule
then collides with one molecule of CO and reacts quickly to
produce one molecule each of NO2 and CO2. The first step is
the slower of the two and is therefore the rate-determining
step. We can write the rate law from this rate-determining
step, which has two molecules of NO2 as the reactants.
R = k[NO2]2
The rate law does not include [CO] because CO reacts after
2NO2 NO3 + NO the rate-determining step and does not affect the rate.
576 CHAPTER 17
SAMPLE PROBLEM D For more help, go to the Math Tutor at the end of this chapter.
Nitrogen dioxide and fluorine react in the gas phase according to the following equation.
2NO2(g) + F2(g) ⎯→ 2NO2F(g)
A proposed mechanism for this reaction follows.
Step 1: NO2 + F2 ⎯→ NO2F + F (slow)
Step 2: F + NO2 ⎯→ NO2F (fast)
Identify the rate-determining step, and write an acceptable rate law.
SOLUTION If we combine these two steps, the intermediate, F, cancels out and we are left with
the original equation. The first step is the slower step, and is considered the rate-
determining step. We can write the rate law from this rate-determining step.
R = k [NO2][F2]
SAMPLE PROBLEM E
A reaction involving reactants X and Y was found to occur by a one-step mechanism:
X + 2Y ⎯→ XY2. Write the rate law for this reaction, and then determine the effect
of each of the following on the reaction rate:
a. doubling the concentration of X
b. doubling the concentration of Y
c. using one-third the concentration of Y
SOLUTION Because the equation represents a single-step mechanism, the rate law can be written
from the equation (otherwise, it could not be). The rate will vary directly with the concentra-
tion of X, which has an implied coefficient of 1 in the equation. And the rate will vary direct-
ly with the square of the concentration of Y, which has the coefficient of 2: R = k[X][Y]2.
a. Doubling the concentration of X will double the rate (R = k[2X][Y]2).
b. Doubling the concentration of Y will increase the rate fourfold (R = k[X][2Y]2).
c. Using one-third the concentration of Y will reduce the rate to one-ninth of its original
value (R = k[X][ 1 Y]2).
3
1. The rate of a hypothetical reaction involving L and M is found to

double when the concentration of L is doubled and to increase
fourfold when the concentration of M is doubled. Write the rate
law for this reaction.
2. At temperatures below 498 K, the following reaction takes place.
NO2(g) + CO(g) ⎯→ CO2(g) + NO(g)
Doubling the concentration of NO2 quadruples the rate of CO2
formed if the CO concentration is held constant. However, dou- that ask you to
bling the concentration of CO has no effect on the rate of CO2 determine rate laws and
formation. Write a rate-law expression for this reaction. effects on reaction rates.
Keyword: HC6RXKX

Wear safety goggles and an apron.
Materials
Factors Influencing Reaction Rate • Bunsen burner
• paper ash
Question 3. To one test tube, add 10 mL of • copper foil strip
How do the type of reactants, vinegar; to a second, add 5 mL • graduated cylinder, 10 mL
surface area of reactants, of vinegar plus 5 mL of water; • magnesium ribbon
concentration of reactants, and to a third, add 2.5 mL of • matches
and catalysts affect the rates vinegar plus 7.5 mL of water. • paper clip
of chemical reactions? To each of the three test tubes,
• sandpaper
add a 3 cm piece of magne-
sium ribbon. • steel wool
Procedure • 2 sugar cubes
Remove all combustible material 4. Using tongs, hold a sugar cube • white vinegar
from the work area. Wear safety and try to ignite it with a
goggles and an apron. Record all • zinc strip
match. Then try to ignite it in a
your results in a data table. burner flame. Rub paper ash • 6 test tubes, 16 × 150 mm
on a second cube, and try to • tongs
1. Add 10 mL of vinegar to each
of three test tubes. To one test ignite it with a match.
tube, add a 3 cm piece of
magnesium ribbon; to a sec- Discussion
ond, add a 3 cm zinc strip; and
to a third, add a 3 cm copper 1. What are the rate-influencing
strip. (All metals should be the factors in each step of the
same width.) If necessary, pol- procedure?
ish the metals with sandpaper 2. What were the results from
until they are shiny. each step of the procedure?
2. Using tongs, hold a paper clip How do you interpret each
in the hottest part of the burn- result?
er flame for 30 s. Repeat with a
ball of steel wool 2 cm in
diameter.
SECTION REVIEW 4. What is meant by a rate law for a chemical

1. What is studied in the branch of chemistry that is reaction? Explain the conditions under which
known as chemical kinetics? a rate law can be written from a chemical
equation. When can a rate law not be written
2. List five important factors that influence the rate from a single step?
of chemical reactions.
Critical Thinking
3. What is a catalyst? Explain the effect of a catalyst 5. RELATING IDEAS Using the ideas of reaction ki-
on the rate of chemical reactions. How does a netics, explain the purpose of food refrigeration.
catalyst influence the activation energy required
by a particular reaction?
578 CHAPTER 17
Catalytic Converters
To see an important example of het- Catalytic converters use pre-
erogeneous catalysis, you do not cious metal catalysts to change
need to look any farther than the the gases coming from the
streets near your home. The catalytic engine into less harmful gases.
converter, an important part of a A combination of rhodium and
vehicle’s exhaust system, uses metal platinum, and sometimes palla-
catalysts to reduce harmful gaseous dium, is used to convert nitro-
pollutants. gen compounds back into N2 and O2. The ceramic honeycomb inside a cat-
In an automobile engine, hydrocar- This combination also converts CO alytic converter is coated with a metal
bon molecules in gasoline or diesel into CO2 and converts VOCs into CO2 catalyst.
fuel undergo a combustion reaction and water. The catalysts need O2
with oxygen from air to make carbon from the air and temperatures above Catalysts that work at lower temper-
dioxide, CO2, and water. The correct approximately 500°F to work proper- atures would reduce an automobile’s
stoichiometric ratio of fuel to oxygen ly. The temperatures are achieved emission during the first few minutes
is required for the fuel to be com- from the normal operation of the car of operation. Other gases that are
pletely burned in the reaction. engine. However, until the car engine emitted by cars may also pose prob-
Additional reaction products are reaches the temperatures needed for lems for the environment. Nitrous
formed when not enough oxygen or the catalysts to work, CO, NOx, and oxide, N2O, can be formed from the
excess oxygen is present. These prod- VOCs will be released into the air by incomplete reduction of NOx in cat-
ucts include carbon monoxide, CO, the automobile. alytic converters. Unlike the NOx
and NOx compounds, such as nitric The interior structure of a catalytic gases, N2O can travel to the upper
oxide, NO, and nitrogen dioxide, NO2. converter is usually made of a atmosphere, where it can destroy
There is also leftover unburned fuel, ceramic honeycomb with a surface ozone. As a greenhouse gas, N2O is
which is called a volatile organic coating of metal catalyst particles. more that 300 times more potent
compound (VOC). The honeycomb has many holes for than CO2.
The Clean Air Act, enacted in the gases to pass through and pro-
1990, regulates automobile emis- vides a large surface area for the Questions
sions of CO, NOx, and VOCs. Without metal to be deposited on. A large 1. Why do you think a heteroge-
a catalytic converter, a car would surface area is needed to maximize neous catalyst is used instead of
release all of the byproducts of the reactions that occur during het- homogeneous catalyst in a cat-
incomplete combustion into the erogeneous catalysis because the alytic converter?
atmosphere. In addition to being transformation of the gas molecules
harmful themselves, NOx com- occurs at the surface of the metal. 2. Nitrous oxide, N2O, actually has
pounds, CO, and VOCs react with Up to 90% of CO, NOx, and VOCs beneficial uses, despite its role as
sunlight to make ozone, O3. In the are typically eliminated from auto- a greenhouse gas. Can you name
lower atmosphere, ozone is a major mobile exhaust by a catalytic con- a beneficial use of N2O?
part of photochemical smog. NOx verter. Although catalytic converters
gases can also mix with rainwater to are beneficial to our environment,
produce acid rain. they could still be improved.

CHAPTER HIGHLIGHTS
The Reaction Process
Vocabulary • The step-by-step process by which an overall chemical reaction
reaction mechanism occurs is called the reaction mechanism.
intermediate • In order for chemical reactions to occur, the particles of the
homogenous reaction reactants must collide.
collision theory • Activation energy is needed to merge valence electrons and to
activation energy loosen bonds sufficiently for molecules to react.
activated complex • An activated complex is formed when an effective collision
between molecules of reactants raises the internal energy to
the minimum level necessary for a reaction to occur.
Reaction Rate
Vocabulary • The rate of reaction is influenced by the following factors:
reaction rate heterogeneous nature of reactants, surface area, temperature, concentration of
chemical kinetics catalyst reactants, and the presence of catalysts.
heterogeneous rate law • The rates at which chemical reactions occur can sometimes be
reactions order experimentally measured and expressed in terms of math-
catalyst rate-determining step ematical equations called rate laws.
catalysis • Rate laws are determined by studying how reaction rate
homogeneous depends on concentration.
catalyst
580 CHAPTER 17
CHAPTER REVIEW
The Reaction Process PRACTICE PROBLEMS

SECTION 1 REVIEW 6. For each of the energy diagrams provided
1. a. What is the collision theory? below, label the reactants, products, ΔE, Ea, and
b. According to this theory, what two conditions Ea′. Also determine the values of ΔE for the
must be met for a collision between reactant forward and reverse reactions, and determine
molecules to be effective in producing new the values of Ea and Ea′. (Hint: See Sample
chemical species? Problem A.)
2. a. What condition must be met for an activated a.
complex to result from the collision of reac-
tant particles? 80
b. Where, in terms of energy, does the activated
60
Energy (kJ/mol)
complex occur along a typical reaction
pathway? 40
3. In a reversible reaction, how does the activation 20
energy required for the exothermic change
0
compare with the activation energy required
for the endothermic change? −20
4. Would you expect the following equation to
represent the mechanism by which propane,
Forward Reverse
C3H8, burns? Why or why not?
C3H8(g) + 5O2(g) ⎯→ 3CO2(g) + 4H2O(g) b.
5. The decomposition of nitrogen dioxide
20
2NO2 ⎯→ 2NO + O2 occurs in a two-step
sequence at elevated temperatures. The first 0
Energy (kJ/mol)
step is NO2 ⎯→ NO + O. Predict a possible

second step that, when combined with the first −20
step, gives the complete reaction.
−40
−60
Forward Reverse
c.
70
60
Energy (kJ/mol)
50
40
30
20
10
0
Forward Reverse

CHAPTER REVIEW
7. Draw and label energy diagrams that depict the c. If the initial concentrations of both A and B
following reactions, and determine all remaining are 0.30 M, at what initial rate is C formed?
values. Place the reactants at energy level zero. d. What is the order of the reaction with
a. ΔEforward = −10 kJ/mol Ea′ = 40 kJ/mol respect to A?
b. ΔEforward = −95 kJ/mol Ea = 20 kJ/mol e. What is the order of the reaction with
c. ΔEreverse = −40 kJ/mol Ea′ = 30 kJ/mol respect to B?
Reaction Rate MIXED REVIEW

SECTION 2 REVIEW 13. Draw and label energy diagrams that depict the
8. Define the rate-determining step for a chemical following reactions, and determine all remaining
reaction. values. Place the reactants at energy level zero.
9. Write the general equation for the rate law, and a. ΔE = +30 kJ/mol Ea′ = 20 kJ/mol
label the various factors. b. ΔE = −30 kJ/mol Ea = 20 kJ/mol
14. A particular reaction is found to have the fol-
PRACTICE PROBLEMS lowing rate law.
R = k[A][B]2
10. a. Determine the overall balanced equation for
How is the rate affected by each of the follow-
a reaction that has the following proposed
ing changes?
mechanism, and write an acceptable rate law.
a. The initial concentration of A is cut in half.
(Hint: See Sample Problem C.)
b. The initial concentration of B is tripled.
Step 1: B2 + B2 ⎯→ E3 + D slow
c. The concentration of A is doubled, but the
Step 2: E3 + A ⎯→ B2 + C2 fast
concentration of B is cut in half.
b. Give the order of the reaction with respect to
d. A catalyst is added.
each reactant.
15. For each of the following pairs, choose the sub-
c. What is the overall order of the reaction?
stance or process that you would expect to react
11. A reaction that involves reactants A and B is
more rapidly.
found to occur in the one-step mechanism:
a. granulated sugar or powdered sugar
2A + B ⎯→ A2B. Write the rate law for this
b. zinc in HCl at 298.15 K or zinc in HCl at
reaction, and predict the effect of doubling the
320 K
concentration of either reactant on the overall
c. 5 g of thick platinum wire or 5 g of thin plati-
reaction rate. (Hint: See Sample Problem C.)
num wire
12. A chemical reaction is expressed by the bal-
16. The following data relate to the reaction
anced chemical equation A + 2B ⎯→ C. Three
A + B ⎯→ C. Find the order with respect
reaction-rate experiments yield the following
to each reactant.
data.
[A] (M) [B] (M) Rate (M/s)
Experiment Initial Initial Initial rate of
number [A] [B] formation of C 0.08 0.06 0.012
0.08 0.03 0.006
1 0.20 M 0.20 M 2.0 × 10−4 M/min
0.04 0.06 0.003
2 0.20 M 0.40 M 8.0 × 10−4 M/min
3 0.40 M 0.40 M 1.6 × 10−3 M/min
a. Determine the rate law for the reaction.

b. Calculate the value of the specific rate
constant.
582 CHAPTER 17
CHAPTER REVIEW
CRITICAL THINKING ALTERNATIVE ASSESSMENT

17. Predicting Outcomes The balanced equation 22. Boilers are sometimes used to heat large build-
for a rapid homogeneous reaction between two ings. Deposits of CaCO3, MgCO3, and FeCO3
gases is as follows: 4A + B ⎯→ 2C + 2D. can hinder the boiler operation. Aqueous solu-
Because the simultaneous collision of four mol- tions of hydrochloric acid are commonly used to
ecules of one reactant with one molecule of the remove these deposits. The general equation for
other reactant is extremely improbable, what the reaction is written below.
would you predict about the nature of the reac- MCO3(s) + 2H3O+(aq) ⎯→
tion mechanism for this reaction system? M2+(aq) + 3H2O(l) + CO2(g)
18. Evaluating Ideas In the equation, M stands for Ca, Mg, or Fe.
a. How can you justify calling the reaction Design an experiment to determine the effect of
pathway that is shown in Figure 4 the various HCl concentrations on the rates of this
minimum-energy pathway for reaction? reaction. Present your design to the class.
b. What significance is associated with the
maximum-energy region of this minimum-
energy pathway?
19. Applying Models Explain why there is a dan- Graphing Calculator
ger of explosion in places such as coal mines, Reaction Orders
sawmills, and grain elevators, where large Go to go.hrw.com for a graphing calculator
amounts of dry, powdered combustible materi- exercise that asks you to calculate the order
als are present. of a reaction from the reaction rates and
concentrations.
20. Evaluating Methods What property would
you measure to determine the reaction rate for Keyword: HC6RXKX
the following reaction? Justify your choice.
2NO2(g) ⎯→ N2O4(g)
RESEARCH & WRITING

21. Look for situations around your house in which
processes are speeded up by an increase in
temperature or slowed down by a decrease in
temperature. Make a list, and discuss the differ-
ent processes.

Math Tutor WRITING RATE LAWS
Factors such as surface area and temperature affect the rate of reactions because they
affect the frequency and energy of collisions between particles. The concentrations of
reactants can also affect the frequency of collisions. If other factors are kept constant,
the rates of most chemical reactions will be determined by the concentrations of reac-
tants. Thus, it is possible to write an equation called a rate law that relates the rate of a
reaction to the concentrations of reactants.
SAMPLE
Fluorine gas reacts with chlorine dioxide according to the following equation.
F2(g) + 2ClO2(g) ⎯→ 2FClO2(g)
Use the following experimental data to write a rate law for this reaction.
Trial Concentration of F2 Concentration of Cl02 Rate (mol/L•s)

1 0.10 M 0.10 M 1.1 × 10−3
2 0.20 M 0.10 M 2.2 × 10−3
3 0.10 M 0.20 M 2.2 × 10−3
4 0.20 M 0.20 M 4.4 × 10−3
To write the rate law, first examine the data to see how the rate of reaction changes as the
concentrations of the reactants change.
• When [F2] doubles and [ClO2] remains constant, the rate of reaction doubles from 1.1 ×
10−3 mol/L • s to 2.2 × 10−3 mol/L • s. So, the rate is directly proportional to [F2], or R α [F2].
• When [ClO2] doubles and [F2] remains constant, the rate of reaction also doubles from
1.1 × 10−3 mol/L • s to 2.2 × 10−3 mol/L • s. So, the rate is directly proportional to [ClO2], or
R α [ClO2].
• Because rate is proportional to both [F2] and [ClO2], you can write the rate law
R = k[F2][ClO2]. The data from Trial 4 help confirm the rate law because when both [F2]
and [ClO2] double, the rate increases by a factor of four, from 1.1 × 10−3 mol/L • s to
4.4 × 10−3 mol/L • s.
PRACTICE PROBLEMS
1. Nitrogen monoxide and oxygen react to 2. Hydrogen reacts with ethyne, C2H2, to pro-
produce nitrogen dioxide according to the duce ethane, C2H6, as shown below:
following equation: 2H2(g) + C2H2(g) ⎯→ C2H6(g)
O2(g) + 2NO(g) ⎯→ 2NO2(g) Use the data in the following table to write a
Use the data in the following table to write a rate law for this reaction.
rate law for this reaction.
Trial [O2] [NO] Reaction Rate Trial [H2] [C2H2] Reaction Rate
(mol/L•s) (mol/L•min)
1 1.20 × 10−2 M 1.40 × 10−2 M 3.30 × 10−3 1 0.20 M 0.20 M 1.5 × 10−4
2 2.40 × 10−2 M 1.40 × 10−2 M 6.60 × 10−3 2 0.40 M 0.20 M 3.0 × 10−4
3 1.20 × 10−2 M 2.80 × 10−2 M 1.32 × 10−2 3 0.20 M 0.40 M 1.5 × 10−4
584 CHAPTER 17
Standardized Test Prep
Answer the following items on a separate piece of paper. 7. In a graph of how energy changes with reaction
MULTIPLE CHOICE
progress, the activated complex appears at the
A. left end of the curve.
1. The sequence of steps that occurs in a reaction B. right end of the curve.
process is called the
C. bottom of the curve.
A. order of the reaction.
D. peak of the curve.
B. rate law.
C. overall reaction. 8. The slowest step in a mechanism is called
D. reaction mechanism. A. the rate-determining step.
B. the uncatalyzed reaction.
2. To be effective, a collision requires
C. the activation step.
A. enough energy only.
D. None of the above
B. favorable orientation only.
C. enough energy and a favorable orientation. 9. A certain reaction is zero order in reactant A
D. a reaction mechanism. and second order in reactant B. What happens
to the reaction rate when the concentrations of
3. How does the energy of the activated complex both reactants are doubled?
compare with the energies of the reactants and A. The reaction rate remains the same.
products? B. The reaction increases by a factor of two.
A. It is lower than both the energy of the reac- C. The reaction rate increases by a factor of four.
tants and the energy of the products. D. The reaction rate increases by a factor of eight.
B. It is lower than the energy of the reactants
but higher than the energy of the products. SHORT ANSWER
C. It is higher than the energy of the reactants 10. Two molecules collide but bounce apart
but lower than the energy of the products. unchanged. What two reasons could account for
D. It is higher than both the energy of the reac- their failure to react?
tants and the energy of the products. 11. Sketch a diagram that shows how the energy
4. If a collision between molecules is very gentle, changes with the progress of an endothermic
the molecules are reaction. Label the curve “Reactants,”
A. more likely to be oriented favorably. “Products,” and “Activated complex.” On the
B. less likely to be oriented favorably.
same diagram, sketch a second curve to show
the change caused by a catalyst.
C. likely to react.
D. likely to rebound without reacting. EXTENDED RESPONSE
5. A species that changes the rate of a reaction but 12. Suggest ways of measuring the concentration of
is neither consumed nor changed is a reactant or product in a reaction mixture.
A. a catalyst. 13. Why are reaction orders not always equal to the
B. an activated complex. coefficients in a balanced chemical equation?
C. an intermediate.
D. a reactant.
6. A rate law relates
A. reaction rate and temperature.
B. reaction rate and concentration.
C. temperature and concentration.
D. energy and concentration. Sometimes, only one part of a
graph or table is needed to answer a question. In
such cases, focus on only the information that is
required to answer the question.

MICRO-
CHAPTER LAB L A B
Rate of a Chemical Reaction

OBJECTIVES BACKGROUND
• Prepare and observe several different In this experiment, you will determine the rate of the
reaction mixtures. reaction whose net equation is written as follows:
+
• Demonstrate proficiency in measuring 3Na2S2O5(aq) + 2KIO3(aq) + 3H2O(l) ⎯→
H
reaction rates. 2KI(aq) + 6NaHSO4(aq)

• Relate experimental results to a rate law One way to study the rate of this reaction is to
that can be used to predict the results of observe how fast Na2S2O5 is used up. After all the
various combinations of reactants. Na2S2O5 solution has reacted, the concentration of
iodine, I2, an intermediate in the reaction, increases.
MATERIALS A starch indicator solution, added to the reaction
• 8-well microscale reaction strips, 2 mixture, will change from clear to a blue-black color
• distilled or deionized water in the presence of I2.
In the procedure, the concentrations of the reac-
• fine-tipped dropper bulbs or small tants are given in terms of drops of solution A and
microtip pipets, 3 drops of solution B. Solution A contains Na2S2O5,
• solution A the starch indicator solution, and dilute sulfuric acid
to supply the hydrogen ions needed to catalyze the
• solution B
reaction. Solution B contains KIO3. You will run the
• stopwatch or clock with second hand reaction with several different concentrations of the
reactants and record the time it takes for the
blue-black color to appear.
SAFETY
For review of safety, please see the Safety in the

Chemistry Laboratory in the front of your book.
PREPARATION
1. Prepare a data table with six rows and six
columns. Label the boxes in the first row of the
second through sixth columns “Well 1,” “Well 2,”
“Well 3,” “Well 4,” and “Well 5.” In the first col-
umn, label the boxes in the second through sixth
rows “Time reaction began,” “Time reaction
stopped,” “Drops of solution A,” “Drops of solu-
tion B,” and “Drops of H2O.”
586 CHAPTER 17
2. Obtain three dropper bulbs or small microtip 6. Observe the lower wells. Note the sequence in
pipets, and label them “A,” “B,” and “H2O.” which the solutions react, and record the number
of seconds it takes for each solution to turn a
3. Fill the bulb or pipet A with solution A, the
blue-black color.
bulb or pipet B with solution B, and the bulb
or pipet for H2O with distilled water.
CLEANUP AND DISPOSAL
PROCEDURE 7. Dispose of the solutions in the container
designated by your teacher. Wash your
1. Using the first 8-well strip, place five drops of
hands thoroughly after cleaning up the
solution A into each of the first five wells.
area and equipment.
Record the number of drops in the appropriate
places in your data table. For the best results,
ANALYSIS AND INTERPRETATION
try to make all drops about the same size.
1. Organizing Data: Calculate the time elapsed for
2. In the second 8-well reaction strip, place one the complete reaction of each combination of
drop of solution B in the first well, two drops in solutions A and B.
the second well, three drops in the third well, four
drops in the fourth well, and five drops in the 2. Evaluating Data: Make a graph of your results.
fifth well. Record the number of drops in your Label the x-axis “Number of drops of solution
data table. B.” Label the y-axis “Time elapsed.” Make a
similar graph for drops of solution B versus rate
3. In the second 8-well strip that contains drops of (1/time elapsed).
solution B, add four drops of water to the first
well, three drops to the second well, two drops 3. Analyzing Information: Which mixture reacted
to the third well, and one drop to the fourth the fastest? Which mixture reacted the slowest?
well. Do not add any water to the fifth well. 4. Evaluating Methods: Why was it important to
4. Carefully invert the second strip. The surface add the drops of water to the wells that contained
tension should keep the solutions from falling fewer than five drops of solution B? (Hint: Figure
out of the wells. Place the strip well-to-well out the total number of drops in each of the
on top of the first strip, as shown in Figure A. reaction wells.)
5. Hold the strips tightly together as shown in CONCLUSIONS

Figure A, and record the exact time, or set the
1. Evaluating Conclusions: Which of the following
stopwatch, as you shake the strips once. This
variables that can affect the rate of a reaction
procedure should mix the upper solutions with
is tested in this experiment: temperature,
each of the corresponding lower ones.
catalyst, concentration, surface area, or nature
of reactants? Explain your answer.
2. Applying Ideas: Use your data and graphs to
determine the relationship between the concen-
tration of solution B and the rate of the reaction.
Describe this relationship in terms of a rate law.
EXTENSIONS
1. Predicting Outcomes: What combination of
drops of solutions A and B would you use if
you wanted the reaction to last exactly 2.5 min?
FIGURE A

CHAPTER 18
Chemical Equilibrium
The creation of stalactites and stalagmites
is the result of a reversible chemical reaction.
Carlsbad Caverns, New Mexico

The Nature of SECTION 1
Chemical Equilibrium OBJECTIVES

Define chemical equilibrium.
Explain the nature of the

equilibrium constant.
I n systems that are in equilibrium, opposing processes occur at the
same time and at the same rate. For example, when an excess of sugar is
placed in water, some sugar molecules go into solution, and others remain Write chemical equilibrium
undissolved. At equilibrium, molecules of sugar are crystallizing at the expressions and carry out
same rate that molecules from the crystal are dissolving.The rate of evap- calculations involving them.
oration of a liquid in a closed vessel can eventually be equaled by the rate
of condensation of its vapor. The resulting equilibrium vapor pressure is
a characteristic of the liquid at the prevailing temperature. The preceding
examples are physical equilibria. In this chapter, we will expand on the
concept of equilibrium to include chemical reactions. You will learn how
a system at equilibrium responds when equilibrium conditions are altered
by changing concentration, pressure, and temperature.
Reversible Reactions
Theoretically, every reaction can proceed in two directions, forward and
reverse. Thus, essentially all chemical reactions are considered to be
reversible under suitable conditions. A chemical reaction in which the
products can react to re-form the reactants is called a reversible reaction.
Mercury(II) oxide decomposes when heated.
Δ
2HgO(s) ⎯→ 2Hg(l) + O2(g)
Mercury and oxygen combine to form mercury(II) oxide when heated

gently.
Δ
2Hg(l) + O2(g) ⎯→ 2HgO(s)
Figure 1 shows both of these reactions taking place. Suppose

mercury(II) oxide is heated in a closed container from which neither the FIGURE 1 When heated, mer-
cury(II) oxide decomposes into its
mercury nor the oxygen can escape. Once decomposition has begun, the
elements, mercury and oxygen.
mercury and oxygen released can recombine to form mercury(II) oxide Liquid mercury reacts with oxygen
again. Thus, both reactions can proceed at the same time. Under these to re-form mercury(II) oxide.
conditions, the rate of the synthesis reaction will eventually equal that of Together these reactions represent
the decomposition reaction. At equilibrium, mercury and oxygen will a reversible chemical process.
CHEMICAL EQUILIBRIUM 589

combine to form mercury(II) oxide at the same rate that mercury(II)
oxide decomposes into mercury and oxygen.The amounts of mercury(II)
oxide, mercury, and oxygen can then be expected to remain constant as
long as these conditions persist. At this point, a state of dynamic equilib-
rium has been reached between the two chemical reactions. Both reac-
tions continue, but there is no net change in the composition of the
system. A reversible chemical reaction is in chemical equilibrium when
the rate of its forward reaction equals the rate of its reverse reaction and
the concentrations of its products and reactants remain unchanged. The
chemical equation for the reaction at equilibrium is written using double
arrows to indicate the overall reversibility of the reaction.
⎯→ 2Hg(l) + O (g)
2HgO(s) ←⎯ 2
Equilibrium, a Dynamic State

Many chemical reactions are reversible under ordinary conditions of
temperature and concentration. They will reach a state of equilibrium
unless at least one of the substances involved escapes or is removed
from the reaction system. In some cases, however, the forward reaction
is so predominant that essentially all reactants will react to form prod-
ucts. Here, the products of the forward reaction are favored, meaning
that at equilibrium there is a much higher concentration of products
than of reactants. Hence, we can say that the equilibrium “lies to the
right,” because products predominate, and products conventionally are
written on the right-hand side of a chemical equation. An example of
such a system is the formation of sulfur trioxide from sulfur dioxide and
oxygen.
⎯→ 2SO (g)
2SO2(g) + O2(g) ←⎯ 3
Notice that the equation is written showing an inequality of the two

arrow lengths. The forward reaction is represented by the longer arrow
to imply that the product is favored in this reaction.
In other cases, the forward reaction is barely under way when the
rate of the reverse reaction becomes equal to that of the forward reac-
tion, and equilibrium is established. In these cases, the amounts of reac-
tants remain high and the amounts of products are low. Here we say
that the equilibrium “lies to the left,” because the reactants are the pre-
dominant species. An example of such a system is the acid-base reaction
between carbonic acid and water.
→ H O+(aq) + HCO−(aq)
H2CO3(aq) + H2O(l) ←⎯ 3 3
In still other cases, both forward and reverse reactions occur to near-
ly the same extent before chemical equilibrium is established. Neither
reaction is favored, and considerable concentrations of both reactants
590 CHAPTER 18
and products are present at equilibrium. An example is the dissociation
of sulfurous acid in water.
⎯→ H O+(aq) + HSO−(aq)
H2SO3(aq) + H2O(l) ←⎯ 3 3
Chemical reactions ordinarily are used to convert available reactants

into more desirable products. Chemists try to convert as much of these
reactants as possible into products. The extent to which reactants are
converted to products is indicated by the numerical value of the equi-
librium constant.
The Equilibrium Expression

Suppose two substances, A and B, react to form products C and D. In
turn, C and D react to produce A and B. Under appropriate conditions,
equilibrium occurs for this reversible reaction. This hypothetical equi-
librium reaction is described by the following general equation.
⎯→ xC + yD
nA + mB ←⎯
Initially, the concentrations of C and D are zero and those of A and

B are maximum. Figure 2 shows that over time the rate of the forward
reaction decreases as A and B are used up. Meanwhile, the rate of the
reverse reaction increases as C and D are formed. When these two reac-
tion rates become equal, equilibrium is established. The individual con-
centrations of A, B, C, and D undergo no further change if conditions
remain the same.
After equilibrium is attained, the concentrations of products and
reactants remain constant, so a ratio of their concentrations should also
Rate Comparison for the Reaction System

⎯→ C + D
A + B ←⎯
A + B ⎯→ C + D
(forward reaction)
Reaction rate
FIGURE 2 Shown are

reaction rates for the hypothetical
Equilibrium
equilibrium reaction system
(forward rate = reverse rate) A + B ←⎯⎯→ C + D. From the time
A and B are mixed together at t0,
the rate of the forward reaction
C + D ⎯→ A + B declines and the rate of the reverse
(reverse reaction) reaction increases until both forward
and reverse reaction rates are equal
at t1, when the equilibrium condition
t0 t1
Time begins.

remain constant. The ratio of the mathematical product [C]x × [D]y to
the mathematical product [A]n × [B]m for this reaction has a definite
value at a given temperature. It is the equilibrium constant of the reac-
tion and is designated by the letter K. The following equation describes
the equilibrium constant for the hypothetical equilibrium system.
The brackets ([ ]) indicate the concentration of each substance as
expressed in mol/L. The superscripts are the coefficients of each sub-
stance in the balanced chemical equation.
[C]x[D]y
K=
[A]n[B]m
The concentrations of substances on the right side of the chemical
equation appear in the numerator of the ratio, with each concentra-
tion raised to a power equal to the coefficient of that substance in the
balanced chemical equation. These substances are the products of the
forward reaction. The concentrations of substances on the left side of
the chemical equation are in the denominator of the ratio, with each
concentration raised to a power equal to the coefficient of that sub-
stance in the balanced chemical equation. These substances are the
reactants of the forward reaction. The constant K is independent of
the initial concentrations. It is, however, dependent on the tempera-
ture of the system.
The Equilibrium Constant

The numerical value of K for a particular equilibrium system is
obtained experimentally. The chemist must analyze the equilibrium
mixture and determine the concentrations of all substances. The value
of K for a given equilibrium reaction at a given temperature shows the
extent to which the reactants are converted into the products of the
reaction. If the value of K is small, the forward reaction occurs only
very slightly before equilibrium is established, and the reactants are
favored. A large value of K indicates an equilibrium in which the orig-
inal reactants are largely converted to products. Only the concentra-
tions of substances that can actually change are included in K. This
means that pure solids and liquids are omitted because their concen-
trations cannot change.
In general, then, the equilibrium constant, K, is the ratio of the math-
ematical product of the concentrations of substances formed at equilib-
rium to the mathematical product of the concentrations of reacting
substances. Each concentration is raised to a power equal to the coeffi-
cient of that substance in the chemical equation. The equation for K is
sometimes referred to as the chemical equilibrium expression.
The H2, I2 , HI Equilibrium System

Consider the reaction between H2 and I2 vapor in a sealed flask at an
elevated temperature. The rate of reaction can be followed by observ-
ing the rate at which the violet color of the iodine vapor diminishes, as
shown in Figure 3. If colorless H2 gas is present in excess, we might
592 CHAPTER 18
expect that the reaction would continue until all of the I2 is used up. The
violet color of the tube would decrease in intensity until all of the iodine
reacts. At that time, the tube would be colorless, because both HI and
the excess H2 are colorless gases.
In actuality, the color fades to a constant intensity but does not dis-
appear completely because the reaction is reversible. Hydrogen iodide
(a)
decomposes to re-form hydrogen and iodine. The rate of this reverse
reaction increases as the concentration of hydrogen iodide increases.
The rate of the forward reaction decreases accordingly. The concentra-
tions of hydrogen and iodine decrease as they react. As the rates of the
opposing reactions become equal, equilibrium is established. The con-
stant color achieved indicates that equilibrium exists among hydrogen,
iodine, and hydrogen iodide. The net chemical equation for the reaction
system at equilibrium follows. (b)
⎯→ 2HI(g)
H2(g) + I2(g) ←⎯
From this chemical equation, the following chemical equilibrium expres-

sion can be written. The concentration of HI is raised to the power of 2
because the coefficient of HI in the balanced chemical equation is 2.
(c)
[HI]2
K= FIGURE 3 Hydrogen iodide gas is
[H2][I2]
produced from gaseous hydrogen
Chemists have carefully measured the concentrations of H2, I2, and and iodine. The violet color of iodine
HI in equilibrium mixtures at various temperatures. In some experi- gas (a) becomes fainter as the reac-
ments, the flasks were filled with hydrogen iodide at known pressure. tion consumes the iodine (b). The
The flasks were held at fixed temperatures until equilibrium was estab- violet does not disappear but reach-
es a constant intensity when the
lished. In other experiments, hydrogen and iodine were the original sub-
reaction reaches equilibrium (c).
stances. Experimental data, together with the calculated values for K,
are listed in Table 1. Experiments 1 and 2 began with hydrogen iodide.
Experiments 3 and 4 began with hydrogen and iodine. Note the close
agreement obtained for the numerical values of the equilibrium con-
stant in all cases.
At 425°C, the equilibrium constant for this equilibrium reaction sys-
tem has the average value of 54.34. This value for K is constant for
any system of H2, I2, and HI at equilibrium at this temperature. If the
TABLE 1 Typical Equilibrium Concentrations of H2, I2, and HI in mol/L at 425°C

[HI]2
K=
Experiment [H2] [I2] [HI] [H2][I2]
1 0.4953 × 10−3 0.4953 × 10−3 3.655 × 10−3 54.46
2 1.141 × 10−3 1.141 × 10−3 8.410 × 10−3 54.33
3 3.560 × 10−3 1.250 × 10−3 15.59 × 10−3 54.62
4 2.252 × 10−3 2.336 × 10−3 16.85 × 10−3 53.97

calculation for K yields a different result, there must be a reason. Either
the H2, I2, and HI system has not reached equilibrium or the system is
not at 425°C.
The balanced chemical equation for an equilibrium system is neces-
sary to write the expression for the equilibrium constant. The data in
Table 1 show that the validity of this expression is confirmed when the
actual values of the equilibrium concentrations of reactants and prod-
ucts are determined experimentally. The values of K are calculated from
these concentrations. No information concerning the kinetics of the
reacting systems is required.
Once the value of the equilibrium constant is known, the equilibrium-
constant expression can be used to calculate concentrations of reactants
or products at equilibrium. Suppose an equilibrium system at 425°C is
found to contain 0.015 mol/L each of H2 and I2. To find the concentra-
tion of HI in this system, rearrange the chemical equilibrium expression
as shown in the two equations that follow.
[HI]2
K=
[H2][I2]
[HI] = K
[H
2][I
2]
Using the known K value and the given concentrations for H2 and I2,
solve the equation for [HI].
[HI] = 0.01
5×0.0
15
×54.
34

[HI] = 0.11 mol/L
An equilibrium mixture of N2 , O2 , and NO gases at 1500 K is determined to consist of 6.4 10–3 mol/L
of N2, 1.7 10–3 mol/L of O2, and 1.1 10–5 mol/L of NO. What is the equilibrium constant for the sys-
tem at this temperature?
SOLUTION
1 ANALYZE Given: [N2] = 6.4 × 10−3 mol/L
[O2] = 1.7 × 10−3 mol/L
[NO] = 1.1 × 10−5 mol/L
Unknown: K
2 PLAN ⎯→ 2NO(g).
The balanced chemical equation is N2(g) + O2(g) ←⎯
[NO]2
The chemical equilibrium expression is K = .
[N2][O2]
3 COMPUTE Substitute the given values for the concentrations into the equilibrium expression.
(1.1 × 10−5 mol/L)2
K= = 1.1 × 10−5
(6.4 × 10−3 mol/L)(1.7 × 10−3 mol/L)
594 CHAPTER 18
4 EVALUATE The value of K is small, which is consistent with more N2 and O2 being present at equilibri-
um than NO. The answer has the correct number of significant figures and is close to an
estimated value of
(1 × 10−5)2
8 × 10−6, calculated as .
(6 × 10−3)(2 × 10−3)
1. At equilibrium a mixture of N2, H2, and NH3 gas at 500°C is deter-

mined to consist of 0.602 mol/L of N2, 0.420 mol/L of H2, and
0.113 mol/L of NH3. What is the equilibrium constant for the reac-
⎯→ 2NH (g) at this temperature?
tion N2(g) + 3H2(g) ←⎯ 3
⎯→
2. The reaction AB C(g) ←⎯ B (g) + AC(g) reached equilibrium
2 2
at 900 K in a 5.00 L vessel. At equilibrium 0.084 mol of AB2C,
0.035 mol of B2, and 0.059 mol of AC were detected. What is the
equilibrium constant at this temperature for this system? (Don’t
forget to convert amounts to concentrations.)
3. A reaction between gaseous sulfur dioxide and oxygen gas to pro-
duce gaseous sulfur trioxide takes place at 600°C. At that temper-
ature, the concentration of SO2 is found to be 1.50 mol/L, the
concentration of O2 is 1.25 mol/L, and the concentration of SO3 is Go to go.hrw.com for
3.50 mol/L. Using the balanced chemical equation, calculate the more practice problems
equilibrium constant for this system. that ask you to calculate
equilibrium constants.
Keyword: HC6EQUX
SECTION REVIEW 7. At equilibrium at 2500 K, [HCl] = 0.0625 mol/L

1. What is meant by chemical equilibrium? and [H2] = [Cl2] = 0.00450 mol/L for the reaction
⎯→ 2HCl(g). Find the value of K.
H2(g) + Cl2(g) ←⎯
2. What is an equilibrium constant?
8. An equilibrium mixture at 425°C is found to con-
3. How does the value of an equilibrium constant sist of 1.83 × 10−3 mol/L of H2, 3.13 × 10−3
relate to the relative quantities of reactants and mol/L of I2, and 1.77 × 10−2 mol/L of HI.
products at equilibrium? Calculate the equilibrium constant, K, for the
4. What is meant by a chemical equilibrium ⎯→ 2HI(g ).
reaction H2(g ) + I2(g ) ←⎯
expression? ⎯→ 2HI(g )
9. For the reaction H2(g ) + I2(g ) ←⎯
5. Hydrochloric acid, HCl, is a strong acid that disso- at 425°C, calculate [HI], given [H2] = [I2] =
ciates completely in water to form H3O+ and Cl −. 4.79 × 10−4 mol/L and K = 54.3.
Would you expect the value of K for the reaction
⎯→ H O+(aq ) + Cl −(aq ) to be
HCl(aq) + H2O(l ) ←⎯ Critical Thinking
3
1 × 10−2, 1 × 10−5, or “very large”? Justify your 10. INFERRING RELATIONSHIPS Use the data from
answer. Experiment 1 in Table 1 to calculate the value
⎯→ H (g ) + I (g).
of K for the reaction 2HI(g ) ←⎯
6. Write the chemical equilibrium expression for the 2 2
⎯→ 2Cl (g ) + 2H O(g ).
reaction 4HCl(g ) + O2(g ) ←⎯ Do you see a relationship between the value you
2 2
obtained and the value in the table?

Fixing the Nitrogen Problem
Historical Perspective
Malthus’s warning seemed to be echoed in the 1840s by
Each year, the chemical industry synthesizes tons of
the great Irish potato famine. In fact, the rest of Europe
nitrogenous fertilizers, increasing agricultural production
likely would have suffered serious food shortages as well
around the globe. But prior to 1915, humans had to rely
had crop yields per acre not been increased through the
solely on natural resources for fertilizer, and the dwindling
use of fertilizers containing nitrogen.
supply of these materials caused widespread fear of world
Few living things can utilize the gas that forms 78% of
starvation. A crisis was averted, however, through the dis-
the atmosphere; they need nitrogen that has been com-
covery of an answer to the “nitrogen problem,” a term
bined with other elements, or “fixed,” to survive.
used at the time to describe the shortage of useful nitro-
But soil often lacks sufficient amounts of the organisms
gen despite its abundance in the atmosphere.
that fix nitrogen for plants, so fertilizers containing usable
The Malthusian Threat nitrogen compounds are added. In 1898, two-thirds of the
In 1798, Thomas Malthus published his famous “Essay on world’s supply of these compounds came from Chile, where
Population,” a report predicting that the world’s food sup- beds of sodium nitrate, or Chile saltpeter, were abundant.
plies could not keep up with the growing human popula- But, as the chemist William Crookes emphasized in his
tion and that famine, death, and misery were inevitable. speech to the British Association that year, these reserves
Nitrogen gas
Animals
Plants
Nitrogen is released when living
things die and also from animal
wastes and plant material. Some
bacteria are able to break the bond
holding the nitrogen molecule
together, freeing the nitrogen
Ammonia atoms to combine with hydrogen to
form ammonia. Plants can absorb
Decomposition the nitrogen in this form from the
Nitrogen-fixing bacteria soil. Animals then benefit from the
on plant roots nitrogen by eating the plants.
596 CHAPTER 18
were limited; it was up to his colleagues to dis-
cover alternatives and prevent Malthus’s dire
forecast from coming true.
The Haber-Nernst Controversy

As early as the 1890s, chemists had shown that
ammonia, a practical source of fixed nitrogen,
could be synthesized at high temperatures and
at atmospheric pressure from elemental hydro-
gen and nitrogen. The problem was that the end
product was present in such minute amounts
that the process was not industrially practical.
In 1904, the German chemist Fritz Haber
seemed to confirm this assessment. He tried react-
ing hydrogen and nitrogen at temperatures of up
Today, ammonia is produced on an industrial scale in plants
to 1020°C using pure iron as well as other metals like this one.
as a catalyst. He found that the amount of ammo-
nia was a mere 0.005% to 0.012% at equilibrium. sures. They also discovered that a catalyst of iron contain-
Haber had apparently closed the door on the synthesis ing small amounts of impurities was an effective replace-
of ammonia from its elements. But in 1906, Walther ment for the rare metals used by Haber.
Nernst, using his new heat theorem, calculated the reac-
An Eerie Epilogue
tion’s theoretical ammonia concentration at equilibria cor-
By September 1913, BASF was producing 20 metric tons of
responding to several pressures. He found that his value at
ammonia a day using the Haber-Bosch process. Eventually,
atmospheric pressure disagreed significantly with Haber’s,
enough ammonia was produced by the chemical industry
and he publicly challenged Haber’s values.
to free Germany and the world of dependence on Chile
Haber was convinced that he was right. He ran the reac-
saltpeter for fertilizer. Chemists had thwarted the
tion at increased pressure to attain an amount of ammo-
Malthusian threat. Yet, the victory proved bittersweet; the
nia that could be measured more accurately.
new ammonia synthesis also became the basis of the pro-
Haber and his assistants confirmed their original find-
duction of nitric acid, used to make many of the explosives
ings, and Nernst later conceded a mathematical error. But
employed in the wars that rocked Europe and the rest of
more important, the new round of experiments indicated
the globe in the first half of the twentieth century.
that a reasonable amount of ammonia might be attained
at pressures of 200 atm (20,000 kPa) using a uranium or
Questions
osmium catalyst.
1. What is the major use for ammonia?
Scaling Up
2. What did Haber find when he tried to synthesize
Large-scale equipment that could withstand such high
ammonia at increased pressure?
pressures was unheard of at the time, and osmium and
uranium were far too scarce to be cost-effective for indus-
try. Nevertheless, in 1909, the German firm BASF bought
the rights to Haber’s findings and put its gifted chemical
engineer Karl Bosch in charge of creating an industrial-
scale system that would make the process profitable.
www.scilinks.org
After nearly five years, Bosch and the company’s chief Topic: Nitrogen
chemist, Alwin Mittasch, succeeded in developing a suit- Code: HC61035
able reactor that could handle the reaction’s high pres-

SECTION 2
Shifting Equilibrium
OBJECTIVES
Discuss the factors that
disturb equilibrium. I n systems that have attained chemical equilibrium, the relative
amounts of reactants and products stay the same. But changes in pres-
Discuss conditions under which sure, concentration, or temperature can alter the equilibrium position
reactions go to completion. and thereby change the relative amounts of reactants and products. By
shifting an equilibrium in the desired direction, chemists can often
improve the yield of the product they are seeking.
Describe the common-ion
effect.
Predicting the Direction of Shift

In 1888, the French chemist Henri Louis Le Châtelier developed a prin-
ciple that provides a means of predicting the influence of stress factors on
equilibrium systems. Le Châtelier’s principle states that if a system at
equilibrium is subjected to a stress, the equilibrium is shifted in the direc-
tion that tends to relieve the stress. This principle is true for all dynamic
equilibria, chemical as well as physical. Changes in pressure, concentra-
tion, and temperature illustrate Le Châtelier’s principle.
Changes in Pressure
A change in pressure affects only equilibrium systems in which gases
are involved. For changes in pressure to affect the system, the total
number of moles of gas on the left side of the equation must be different
from the total number of moles of gas on the right side of the equation.
Let us consider the Haber process for the synthesis of ammonia. Note
that there is a total of four molecules of gas on the reactant side of the
equation and two molecules of gas on the product side of the equation.
⎯→ 2NH (g)
N2(g) + 3H2(g) ←⎯ 3
First, consider an increase in pressure as the applied stress. Can the sys-
tem shift in a way that reduces the stress? Yes. An increase in pressure
causes increases in the concentrations of all species. The system can
reduce the number of molecules, and hence the total pressure, by shift-
ing the equilibrium to the right. For each four molecules of reactants,
nitrogen and hydrogen, there are two molecules of product, ammonia.
By producing more NH3, and using up N2 and H2, the system can reduce
the total number of molecules. This leads to a decrease in pressure.
Although the new equilibrium pressure is still higher than before, it is
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Topic: Haber Process not as high as the pressure caused by the initial stress.
Code: HC60704 An increase in pressure on confined gases causes an increase in the
concentrations of these gases. Even though changes in pressure may
598 CHAPTER 18
shift the equilibrium position, they do not affect the value of the equi- (a) at equilibrium
librium constant.
Ammonia produced in the Haber process is continuously removed by
condensing it to liquid ammonia. This condensation removes most of the N2
product from the gas phase in which the reaction occurs. The resulting
decrease in the partial pressure of NH3 gas in the reaction vessel is a
stress and is the same as a decrease in product concentration, which
shifts the equilibrium to the right.
The introduction of an inert gas, such as helium, into the reaction ves-
sel for the synthesis of ammonia increases the total pressure in the vessel.
But it does not change the partial pressures of the reaction gases present. (b) stressed (not at equilibrium)
Therefore, increasing pressure by adding a gas that is not a reactant or N2 added
a product cannot affect the equilibrium position of the reaction system.
Changes in Concentration
An increase in the concentration of a reactant is a stress on the equilib- H2
rium system. Consider the following hypothetical reaction.
⎯→ C + D
A + B ←⎯
An increase in the concentration of A creates a stress. To relieve the
stress, some of the added A reacts with B to form products C and D. The (c) at new equilibrium
equilibrium is reestablished with a higher concentration of A than before
the addition but a lower concentration of B. Figure 4 illustrates the effect
on a system in equilibrium produced by increasing the concentration of a
NH3
reactant. Similarly, an increase in the concentration of B drives the reac-
tion to the right. An increase in the concentration of either C or D shifts
the equilibrium to the left. A decrease in the concentration of C or D has
the same effect on the position of the equilibrium as does an increase in
the concentration of A or B; the equilibrium shifts to the right.
Changes in concentration have no effect on the value of the equilib-
rium constant. Although concentrations of both reactants and products
⎯→ 2NH (g)
N2(g) + 3H2(g) ←⎯ 3
do change, the new concentrations give the same value of the equilibri-
um constant when equilibrium is reestablished. FIGURE 4 (a) N2, H2, and NH3
Many chemical processes involve heterogeneous reactions in which are in equilibrium within a closed
reactants or products are in different phases. The concentrations of pure system. (b) Addition of more N2
solids and liquids do not change, and by convention are not written in the causes a stress on the initial equilib-
equilibrium expression. Also, when a solvent such as water, in a system rium. (c) The new equilibrium posi-
tion for this system has a higher
involving acids and bases, is in an equilibrium equation, it is not includ-
concentration of N2, a lower concen-
ed in the equilibrium expression. In Chapter 15, the expression for Kw
tration of H2, and a higher concen-
used this convention and the concentration of water is not included in tration of NH3 than initially.
the expression. The reaction representing the self-ionization of water is
⎯→ H O+(aq) + OH−(aq)
2H2O(l) ←⎯ 3
and the equation for Kw is Kw = [H3O+][OH−].

The following equation describes the equilibrium system established
by the decomposition of solid calcium carbonate.
⎯→ CaO(s) + CO (g)
CaCO3(s) ←⎯ 2

The products are a solid and a gas. Because both CaCO3 and CaO are
solids, they are not in the equilibrium constant expression. This leads to
the following expression for the equilibrium constant.
K = [CO2]
Carbon dioxide is the only substance in the system that appears in the
equilibrium expression. Because the total number of moles of gas on
the left side of the equation is different from the total number of moles
on the right side of the equation, pressure changes will affect the equi-
librium. High pressure favors the reverse reaction, which causes CO2
molecules to react with the solid CaO to form solid CaCO3. Low pres-
sure favors the formation of CO2 from the decomposition of CaCO3.
Because both CaO and CaCO3 are solids, changing their amounts will
not change the equilibrium concentration of CO2.
Changes in Temperature
Reversible reactions are exothermic in one direction and endothermic
in the other. Remember, equilibrium constants are for a given temper-
ature because changing the temperature changes the relative amounts
of reactants and products.
Increasing the temperature is, in effect, the addition of enery in the
form of heat. According to Le Châtelier’s principle, the stress of the
added heat will be lessened by shifting the equilibrium in the direction
that removes heat (lowers the temperature). This means that energy
must be absorbed so the reaction that is endothermic occurs until a new
equilibrium is established. Likewise, the removal of energy as a result of
lowering the temperature causes the exothermic reaction to take place.
The synthesis of ammonia by the Haber process is exothermic, as indi-
cated by the energy as heat shown on the product side of the equation.
⎯→ 2NH (g) + 92 kJ
N2(g) + 3H2(g) ←⎯ 3
A high temperature favors the decomposition of ammonia, the

endothermic reaction. But at low temperatures, the forward reaction is
too slow to be commercially useful. The temperature used represents a
compromise between kinetic and equilibrium requirements. It is high
enough that equilibrium is established rapidly but low enough that the
equilibrium concentration of ammonia is significant. Moderate temper-
ature (about 500°C) and very high pressure (700–1000 atm) produce a
satisfactory yield of ammonia.
The production of colorless dinitrogen tetroxide gas, N2O4, from dark
red-brown NO2 gas is also an exothermic reaction. Figure 5 shows how
temperature affects the equilibrium of this system. Figure 5b shows the
NO2/N2O4 equilibrium mixture at 25°C.When the temperature of the sys-
tem is lowered to 0°C, the system experiences a stress (removal of ener-
gy as heat). To counteract this stress, the system shifts to the right, or in
the direction of the exothermic reaction. This shift increases the amount
of colorless N2O4 gas and decreases the amount of brown NO2 gas, as
shown in Figure 5a. Because more N2O4 is present, K is increased. When
the system is heated to 100°C, the added energy is the stress, and the equi-
600 CHAPTER 18
(a) (b) (c)
FIGURE 5 Different temperatures
can cause an equilibrium system to
shift and seek a new equilibrium
position.
0°C 25°C 100°C

Very light brown Medium brown Dark brown
⎯→ N O (g) + energy as heat
2NO2(g) ←⎯ 2 4
(brown) (colorless)
librium shifts to the left, or in the direction of the endothermic reaction.

This shift decreases the amount of colorless N2O4 gas and increases the
amount of brown NO2 gas, as shown in Figure 5c. Because less N2O4 gas
is present, K is decreased. The change in temperature changes the value
of K. For any system in which the forward reaction is an exothermic reac-
tion, increasing the temperature decreases the value of K.
For an endothermic reaction, such as the decomposition of calcium
carbonate, energy as heat shows up on the reactant side of the equation.
⎯→ CaO(s) + CO (g)
556 kJ + CaCO3(s) ←⎯ 2
An increase in temperature caused by adding energy to the system

causes the value of K to increase and the equilibrium to shift to the right.
Catalysts speed up the rate of reactions. So what happens to equilib-
rium concentrations if a catalyst is present? Nothing! When a catalyst is
added to an equilibrium system, it speeds up both the forward and
reverse reactions. The equilibrium concentrations are achieved faster,
but the concentrations and K remain the same.
Reactions That Go to Completion

Some reactions involving compounds formed by the chemical interac-
tion of ions in solutions appear to go to completion in the sense that the
ions are almost completely removed from solution. The extent to which
reacting ions are removed from solution depends on the solubility of
the compound formed and, if the compound is soluble, on the degree of
ionization. Thus, a product that escapes as a gas, precipitates as a solid,
or is only slightly ionized effectively removes from solution the bulk of
the reacting ions that compose it. Consider some specific examples of
situations in which such ionic reactions go to completion.

Formation of a Gas
Reactions that form a gas as a product are one example of reactions
that go to completion. When a strong acid is added to an aqueous solu-
tion of baking soda, or sodium bicarbonate, carbon dioxide is formed.
The net ionic equation shows that ions are removed.
H3O+ + HCO−3 ⎯→ 2H2O(l) + CO2(g)
This reaction goes practically to completion because one of the prod-

ucts, CO2, escapes as a gas if the container is open to the air.
Formation of a Precipitate
When solutions of sodium chloride and silver nitrate are mixed, a white
precipitate of silver chloride immediately forms, as shown in Figure 6.
The overall ionic equation for this reaction follows.
Na+(aq) + Cl −(aq) + Ag+(aq) + NO−3 (aq) ⎯→ Na+(aq) + NO−3 (aq) + AgCl(s)
If chemically equivalent amounts of the two solutes are mixed, only Na+
ions and NO−3 ions remain in solution in appreciable quantities. Almost
all of the Ag+ ions and Cl − ions combine and separate from the solution
as a precipitate of AgCl. The reason is that AgCl is only very slightly
soluble in water. The solution is now a saturated solution of AgCl. The
reaction thus effectively goes to completion because an essentially
insoluble product is formed.
Cl−
Na+ H2O
H2O NO3−
Ag+
NO3−
Ag+
Cl−
Na+
FIGURE 6 When a clear sodium
H2O
chloride solution is combined with
a clear solution of silver nitrate, an
insoluble white precipitate of silver
chloride is formed. AgCl
602 CHAPTER 18
Formation of a Slightly Ionized Product
Neutralization reactions between H3O+ ions from aqueous acids and
OH − ions from aqueous bases result in the formation of water molecules,
which are only slightly ionized. A reaction between HCl and NaOH
illustrates this process. Aqueous HCl supplies H3O+ ions and Cl − ions to
the solution, and aqueous NaOH supplies Na+ ions and OH − ions, as
shown in the following overall ionic equation.
H3O+(aq) + Cl −(aq) + Na+(aq) + OH −(aq) ⎯→ Na+(aq) + Cl −(aq) + 2H2O(l)
Neglecting the spectator ions, the net ionic equation is as follows.
H3O+(aq) + OH −(aq) ⎯→ 2H2O(l)
Because it is only slightly ionized, the water exists almost entirely as C ROSS -D ISCIPLINARY
molecules. Thus, hydronium ions and hydroxide ions are almost entirely Go to go.hrw.com for a full-length
removed from the solution. The reaction effectively goes to completion article on equilibrium reactions and
because the product is only slightly ionized. caves.
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Common-Ion Effect
An equilibrium reaction may be driven in the desired direction by
applying Le Châtelier’s principle. Suppose hydrogen chloride gas is
bubbled into a saturated solution of sodium chloride. Hydrogen chlo-
ride is extremely soluble in water, and it is completely ionized.
HCl(g) + H2O(l) ⎯→ H3O+(aq) + Cl −(aq)
The equilibrium for a saturated solution of sodium chloride is described

by the following equation.
⎯→ Na+(aq) + Cl −(aq)
NaCl(s) ←⎯
As the hydrogen chloride dissolves in sufficient quantity, it increases the

concentration of Cl − ions in the solution, which is a stress on the equi-
librium system. The system can compensate, according to Le Châtelier’s
principle, by combining some of the added Cl − ions with an equivalent
amount of Na+ ions. This causes some solid NaCl to precipitate out,
relieving the stress of added chloride. The new equilibrium has a greater
concentration of Cl − ions but a decreased concentration of Na+ ions.
However, the product of [Na+] and [Cl −] still has the same value as
before. This phenomenon, in which the addition of an ion common to
two solutes brings about precipitation or reduced ionization, is an exam-
ple of the common-ion effect.
The common-ion effect is also observed when one ion species of a
weak electrolyte is added in excess to a solution.Acetic acid, CH3COOH,

is such an electrolyte. A 0.1 M CH3COOH solution is only about 1.3%
ionized as hydronium ions and acetate ions, CH3COO−. The ionic equi-
librium is shown by the following equation.
⎯→ H O+(aq) + CH COO−(aq)
CH3COOH(aq) + H2O(l) ←⎯ 3 3
Addition of sodium acetate, NaCH3COO (an ionic salt that is soluble in

FIGURE 7 The solution of
CH3COOH on the left is combined water), to a solution containing acetic acid increases the acetate ion con-
with the solution of NaCH3COO in centration. The equilibrium then shifts in the direction that uses up some
the center. Both contain the com- of the added acetate ions in accordance with Le Châtelier’s principle.
mon ion, CH3COO−. They produce More molecules of acetic acid are formed, and the concentration of
the solution on the right, which hydronium ions is reduced. In general, the addition of a salt with an ion
is only slightly acidic due to the in common with the weak electrolyte reduces the ionization of the elec-
decreased ionization of the acid. The
trolyte. Figure 7 shows a 0.25 M CH3COOH solution on the left that has
colors of the solutions are due to the
addition of an acid-base indicator.
a pH of about 2.7.
Mixing that with the
0.10 M NaCH3COO
solution in the center
produces the solution
on the right, which has
a pH of about 4.5, indi-
cating lower [H3O+] and
thus lowered acetic acid
ionization.
SECTION REVIEW 5. Predict the effect that decreasing pressure would

1. Name three ways the chemical equilibrium can be have on each of the following reaction systems at
disturbed. equilibrium.
⎯→ 2HCl(g )
a. H (g ) + Cl (g) ←⎯
2. Describe three situations in which ionic reactions 2 2
go to completion. ⎯→ NH (g ) + HCl(g )
b. NH4Cl(s) ←⎯ 3
3. Describe the common-ion effect. ⎯→ 2H O(l ) + O (g )
c. 2H2O2(aq ) ←⎯ 2 2
4. Identify the common ion in each of the following ⎯→ 2O (g )
d. 3O2(g ) ←⎯ 3
situations.
Critical Thinking
a. 5 g of NaCl is added to a 2.0 M solution of HCl
6. PREDICTING OUTCOMES Carbon dioxide and water
b. 50 mL of 1.0 M NaCH3COO is added to 1.0 M react to form bicarbonate ion and hydronium ion.
CH3COOH Hyperventilation (rapid breathing) causes more car-
c. 1 g of NH4Cl is added to 100 mL of aqueous NH3 bon dioxide to be exhaled than normal. How will
hyperventilation affect the pH of blood? Explain.
604 CHAPTER 18
Equilibria of Acids, SECTION 3
Bases, and Salts OBJECTIVES

Explain the concept of
acid ionization constants,
and write acid ionization
equilibrium expressions.
Ionization Constant of a Weak Acid Review the ionization

constant of water.
About 1.3% of the solute molecules in a 0.1 M acetic acid solution are
ionized at room temperature. The remaining 98.7% of the acetic acid
Explain buffering.
molecules, CH3COOH, remain nonionized. Thus, the solution contains
three species of particles in equilibrium: CH3COOH molecules, H3O+
ions, and acetate ions, CH3COO−. From the equilibrium equation for Compare cation and anion
the ionization of acetic acid, the equilibrium constant equation can be hydrolysis.
written.
⎯→ H O+ + CH COO−
CH3COOH + H2O ←⎯ 3 3
[H3O+][CH3COO−]
K=
[CH3COOH][H2O]
Notice that the concentration of water is not included in the equilib-
rium expression. The reason is that water is the solvent, and water mol-
ecules greatly exceed the number of acetic acid molecules. Without
introducing a measurable error, one can assume that the molar concen-
tration of H2O molecules remains constant in such a solution. Thus,
because both K and [H2O] are constant, the product K[H2O] is constant.
[H3O+][CH3COO−]
K[H2O] =
[CH3COOH]
The left side of the equation can be simplified by setting K[H2O] = Ka .
[H3O+][CH3COO−]
Ka =
[CH3COOH]
The term Ka is called the acid ionization constant. The acid ionization
constant, Ka , like the equilibrium constant, K, is constant for a specified
temperature but has a new value for each new temperature.
The acid ionization constant for a weak acid represents a small value.
To determine the numerical value of the ionization constant for acetic
acid at a specific temperature, the equilibrium concentrations of H3O+
ions, CH3COO− ions, and CH3COOH molecules must be known. The
ionization of a molecule of CH3COOH in water yields one H3O+ ion
and one CH3COO− ion. These concentrations can, therefore, be found
experimentally by measuring the pH of the solution.

TABLE 2 Ionization of Acetic Acid
Molarity % ionized [H3O+] [CH3COOH] Ka
0.100 1.33 0.00133 0.0987 1.79 × 10−5
0.0500 1.89 0.000945 0.0491 1.82 × 10−5
0.0100 4.17 0.000417 0.00958 1.81 × 10−5
0.00500 5.86 0.000293 0.00471 1.82 × 10−5
0.00100 12.6 0.000126 0.000874 1.82 × 10−5
Ionization data and constants for some dilute acetic acid solutions at
25°C are given in Table 2. Notice that the numerical value of Ka is
almost identical for each solution molarity shown. The numerical value
of Ka for CH3COOH at 25°C can be determined by substituting numer-
ical values for concentration into the equilibrium equation.
[H3O+][CH3COO−]
Ka =
[CH3COOH]
At constant temperature, an increase in the concentration of CH3COO−

ions through the addition of sodium acetate, NaCH3COO, disturbs the
buffered unbuffered equilibrium, as predicted by Le Châtelier’s principle. This disturbance
(a) causes a decrease in [H3O+] and an increase in [CH3COOH]. Eventually,
the equilibrium is reestablished with the same value of Ka . But there is a
higher concentration of nonionized acetic acid molecules and a lower con-
centration of H3O+ ions than before the extra CH3COO− was added.
Changes in the hydronium ion concentration affect pH. In this example,
the reduction in [H3O+] means an increase in the pH of the solution.
buffered unbuffered
(b)
Buffers
FIGURE 8 (a) The beaker on the
The solution just described contains both a weak acid, CH3COOH, and
left contains a buffered solution and
an indicator with a pH of about 5.
a salt of the weak acid, NaCH3COO. The solution can react with either
The beaker on the right contains an acid or a base. When small amounts of acids or bases are added, the
mostly water with a trace amount of pH of the solution remains nearly constant. The weak acid and the com-
acid and an indicator. The pH meter mon ion, CH3COO−, act as a “buffer” against significant changes in the
shows a pH of 5.00 for this solution. pH of the solution. Because it can resist changes in pH, this solution is a
(b) After 5 mL of 0.10 M HCl is buffered solution. Figure 8 shows how a buffered and a nonbuffered
added to both beakers, the beaker solution react to the addition of an acid.
on the left does not change color,
Suppose a small amount of acid is added to the acetic acid–sodium
indicating no substantial change in
its pH. However, the beaker on the
acetate solution. Acetate ions react with most of the added hydronium
right undergoes a definite color ions to form nonionized acetic acid molecules.
change, and the pH meter shows
a pH of 2.17. CH3COO−(aq) + H3O+(aq) ⎯→ CH3COOH(aq) + H2O(l)
606 CHAPTER 18
The hydronium ion concentration and the pH of the solution remain
practically unchanged.
Suppose a small amount of a base is added to the original solution.
The OH − ions of the base react with and remove hydronium ions to form
nonionized water molecules. Acetic acid molecules then ionize and
mostly replace the hydronium ions neutralized by the added OH− ions.
CH3COOH(aq) + H2O(l) ⎯→ H3O+(aq) + CH3COO−(aq)
The pH of the solution again remains practically unchanged.

A solution of a weak base containing a salt of the base behaves in a
similar manner. The hydroxide ion concentration and the pH of the
solution remain essentially constant with small additions of acids or
bases. Suppose a base is added to an aqueous solution of ammonia that
also contains ammonium chloride. Ammonium ions donate a proton to
the added hydroxide ions to form nonionized water molecules.
NH+4 (aq) + OH −(aq) ⎯→ NH3(aq) + H2O(l)
If a small amount of an acid is added to the solution instead, hydrox- FIGURE 9 Many consumer prod-
ide ions from the solution accept protons from the added hydronium ucts are buffered to protect the body
from potentially harmful pH changes.
ions to form nonionized water molecules. Ammonia molecules in the
solution then ionize and mostly replace the hydroxide ions neutralized
by added H3O+.
NH3(aq) + H2O(l) ⎯→ NH+4 (aq) + OH −(aq)
Buffer action has many important applications in chemistry and

physiology. Human blood is naturally buffered to maintain a pH of
between 7.3 and 7.5. This is essential because large changes in pH would
lead to serious disturbances of normal body functions. Figure 9 shows
an example of one of the many medicines buffered to prevent large and
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potentially damaging changes in pH. Topic: Buffers
Code: HC60195
Ionization Constant of Water

Recall from Chapter 15 that the self-ionization of water is an equilib-
rium reaction.
⎯→ H O+(aq) + OH −(aq)
H2O(l) + H2O(l) ←⎯ 3
Equilibrium is established with a very low concentration of H3O+

and OH − ions. The expression for the equilibrium constant, Kw =
[H3O+][OH −], is derived from the balanced chemical equation. The
numerical value of Kw, obtained experimentally, is 1.0 × 10−14 at 25°C.

Hydrolysis of Salts
Salts are formed during neutralization reactions between acids and
bases. When a salt dissolves in water, it produces positive ions (cations)
of the base from which it was formed and negative ions (anions) of the
acid from which it was formed. Therefore, the solution might be expect-
ed to be neutral. The aqueous solutions of some salts, such as NaCl and
KNO3, are neutral, having a pH of 7. However, when sodium carbonate
dissolves in water, the resulting solution turns red litmus paper blue,
indicating a pH greater than 7. Ammonium chloride produces an aque-
ous solution that turns blue litmus paper red, indicating a pH less than
7. Salts formed from the combination of strong or weak acids and bases
are shown in Figure 10.
The variation in pH values can be accounted for by examining the
ions formed when each of these salts dissociates. If the ions formed are
from weak acids or bases, they react chemically with the water mole-
cules, and the pH of the solution will have a value other than 7. A reac-
tion between water molecules and ions of a dissolved salt is hydrolysis. If
the anions react with water, the process is anion hydrolysis and results
in a more basic solution. If the cations react with water molecules, the
process is cation hydrolysis and results in a more acidic solution.
Anion Hydrolysis
In the Brønsted sense, the anion of the salt is the conjugate base of the
acid from which it was formed. It is also a proton acceptor. If the acid is
weak, its conjugate base (the anion) will be strong enough to remove pro-
(a) (b) (c) (d)
FIGURE 10 The universal indicator shows that the pH of salt solutions

varies, depending on the strength of the acid and the base that formed the salt.
(a) NaCl is formed from a strong acid and a strong base; the color of the indi-
cator shows the pH is neutral. (b) The indicator shows the pH of the sodium
acetate solution is basic. This was formed from a strong base and a weak acid.
(c) The strong acid and weak base combination in ammonium chloride pro-
duces an acidic solution, as shown by the reddish tint of the indicator. (d) The
weak acid and weak base that form ammonium acetate are of comparable
strength. A solution of ammonium acetate is essentially neutral.
608 CHAPTER 18
tons from some water molecules, proton donors, to form OH − ions. An
equilibrium is established in which the net effect of the anion hydrolysis
is an increase in the hydroxide ion concentration, [OH −], of the solution.
The equilibrium equation for a typical weak acid in water, HA, form-
ing hydronium ion and an anion, A−, is as follows.
⎯→ H O+(aq) + A−(aq)
HA(aq) + H2O(l) ←⎯ 3
From this equation, the generalized expression for Ka can be written.

Note that as before, water does not appear in the general equilibrium
equation. Blood Buffers
Blood normally has a pH of 7.4. If the
[H3O+][A−] pH of blood in a human rises above 7.8
Ka =
[HA] or falls below 7.0, this change in pH is
usually fatal. The primary buffer in blood
The hydrolysis reaction between water and the anion, A−, that is pro- is the carbonic acid–bicarbonate ion sys-
duced by the ionization of the weak acid, HA, is represented by the gen- tem, CO2(g) + H2O(l ) ←⎯⎯→ H CO (aq) +
2 3
eral equilibrium equation that follows. HCO−3 (aq). A condition called respiratory
acidosis causes the pH to drop. It is the
⎯→ HA(aq) + OH −(aq)
A−(aq) + H2O(l) ←⎯
result of hypoventilation, or slowed
breathing, the opposite of hyperventila-
tion. Hypoventilation can be caused by
Neutral water has equal concentrations of H3O+ and OH−. Since HA is a congestive heart failure, pneumonia, or
weak acid, the anion A− has a strong attraction for protons. Adding A− to narcotics. Because breathing is slowed,
water in effect attracts (removes) H3O+ in water to form HA. This caus- carbon dioxide accumulates and its
concentration rises. This change causes a
es OH− to increase relative to H3O+ as represented in the equation
shift in the equilibrium to the right due
above. The lower the value of Ka, the stronger the attraction A− will have to Le Châtelier’s principle, and the blood
for protons and the larger the concentration of OH−. In other words, the becomes more acidic because of the
weaker the acid, HA, the stronger its conjugate base, A−. higher concentration of carbonic acid.
Aqueous solutions of sodium carbonate are strongly basic. The so-
dium ions, Na+, in sodium carbonate do not undergo hydrolysis in aque-
ous solution, but the carbonate ions, CO2−3 , react as a Brønsted base. A
CO2−3 anion acquires a proton from a water molecule to form the weak
Brønsted acid, HCO−3 , and the OH − ion.
⎯→ − −
3 (aq) + H2O(l) ←⎯ HCO3 (aq) + OH (aq)
CO2−
The OH − ion concentration increases until equilibrium is established.

Consequently, the H3O+ ion concentration decreases so that the prod-
uct [H3O+][OH −] remains equal to the ionization constant, Kw , of water
at the temperature of the solution. Thus, the pH is higher than 7, and the
solution is basic.
Cation Hydrolysis
In the Brønsted sense, the cation of the salt is the conjugate acid of the
base from which it was formed. It is also a proton donor. If the base is
weak, the cation is an acid strong enough to donate a proton to a water
molecule, a proton acceptor, to form H3O+ ions. An equilibrium is
established in which the net effect of the cation hydrolysis is an increase
in the hydronium ion concentration, [H3O+], of the solution.

The following equilibrium equation for a typical weak base, B, is used
to derive the generalized expression for Kb , the base dissociation
constant.
B(aq) + H O(l) ←⎯⎯→ BH+(aq) + OH −(aq)
2
[BH +][OH −]
Kb =
[B]
The hydrolysis reaction between water and the cation, BH+, produced
by the dissociation of the weak base, B, is represented by the general
equilibrium equation that follows.
⎯→ H O+(aq) + B(aq)
BH+(aq) + H2O(l) ←⎯ 3
In the forward reaction, the cation BH+ donates a proton to the water
molecule to form the hydronium ion. Because H3O+ ions are formed,
the solution must become more acidic, as shown in the equation above.
The extent of H3O+ ion formation depends on the relative strength of
the base B. The weaker the base, the greater the concentration of H3O+
ions will be. Therefore, the weaker the base, the stronger its conjugate
acid.
Ammonium chloride, NH4Cl, dissociates in water to produce NH+4
ions and Cl − ions. Chloride ions are the conjugate base of the strong
acid HCl, so they do not hydrolyze in water. Ammonium ions, however,
are the conjugate acid of a weak base, NH3. Ammonium ions donate
protons to water molecules. Equilibrium is established with an
increased [H3O+], so the pH is lower than 7.
Neutralization Curve for 100 mL

of 0.100 M CH3COOH Titrated with 0.100 M NaOH
13
12
11 4
10
9 Equivalence point 3
8
7
pH
FIGURE 11 At point 1 on the

6 2
titration curve, only acetic acid is
present. The pH depends on the weak 5
acid alone. At 2 there is a mixture of 4 1
CH3COOH and CH3COO−. Adding 3 Buffer region
NaOH changes the pH slowly. At
2
point 3 all acid has been converted
to CH3COO−. This hydrolyzes to 1
produce a slightly basic solution. 0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
At 4 the pH is due to the excess
OH− that has been added. mL NaOH added
610 CHAPTER 18
Hydrolysis in Acid-Base Reactions
Hydrolysis can help explain why the end point of a neutralization reac-
tion can occur at a pH other than 7. The hydrolysis properties of salts
are determined by the relative strengths of the acids and bases from
which the salts were formed. Salts can be placed in four general cate-
gories, depending on their hydrolysis properties: strong acid–strong
base, strong acid–weak base, weak acid–strong base, and weak acid–
weak base.
Salts of strong acids and strong bases produce neutral solutions
because neither the cation of a strong base nor the anion of a strong
acid hydrolyzes appreciably in aqueous solutions. HCl(aq) is a strong
acid, and NaOH(aq) is a strong base. Neither the Na+ cation of the
strong base nor the Cl − anion of the strong acid undergoes hydrolysis in
water solutions. Therefore, aqueous solutions of NaCl are neutral.
Similarly, KNO3 is the salt of the strong acid HNO3 and the strong base
KOH. Measurements show that the pH of an aqueous KNO3 solution is
always very close to 7.
The aqueous solutions of salts formed from reactions between weak
acids and strong bases are basic at the equivalence point, as shown in
Figure 11. Anions of the dissolved salt are hydrolyzed by the water
molecules, and the pH of the solution is raised, indicating that the
hydroxide-ion concentration has increased. Aqueous solutions of sodi-
um acetate, NaCH3COO, are basic. The acetate ions, CH3COO−, under-
go hydrolysis because they are the anions of the weak acid acetic acid.
The cations of the salt are from a strong base, NaOH, and do not
hydrolyze, because NaOH is 100% dissociated.
Figure 12 shows that salts of strong acids and weak bases are acidic
at the equivalence point. Cations of the dissolved salt are hydrolyzed in
Neutralization Curve for 100 mL

of 0.100 M NH3 Titrated with 0.100 M HCl
13
12
11 1 Buffer region
10
9
2
8
7
pH
6 FIGURE 12 At point 1 on the

Equivalence point 3
5 titration curve, only aqueous ammo-
4 nia is present. The pH is determined
3
by the base alone. At 2 there is a
mixture of NH3 and NH +4 . Adding
2 4 HCl changes the pH slowly. At
1 point 3 all aqueous ammonia has
0 been converted to NH +4 . At 4 the
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
pH is determined by the excess
mL HCl added H3O+ that is being added.

the water solvent, and the pH of the solution is lowered, indicating that
the hydronium ion concentration has increased. In this case, the cations
of the salt undergo hydrolysis because they are the positive ions from a
weak base. The anions of the salt are the negative ions from a strong
acid and do not hydrolyze appreciably. Ammonium chloride, NH4Cl, is
a salt that produces an acidic solution.
Salts of weak acids and weak bases can produce either acidic, neu-
tral, or basic aqueous solutions, depending on the salt dissolved. This is
because both ions of the dissolved salt are hydrolyzed extensively. If
both ions are hydrolyzed equally, the solution remains neutral. The ions
in ammonium acetate, NH4CH3COO, hydrolyze equally, producing a
neutral solution, as shown in Figure 10d on page 608.
In salts formed from a weak acid and weak base, the cation and anion
both undergo hydrolysis. For example, when aluminum sulfide is placed
in water, Al3+ reacts with OH– forming Al(OH)3, and S2– reacts with H+
forming H2S. The reaction is symbolized by the following chemical
equation.
Al2S3(s) + 6H2O(l) ⎯→ 2Al(OH)3(s) + 3H2S(g)
Since Al(OH)3 is a precipitate and H2S is a gas, both are removed from
solution.
SECTION REVIEW 7. What is hydrolysis? Compare cation and anion

1. What is meant by an acid ionization constant? hydrolysis.
2. How is an acid ionization equilibrium expression 8. Which of the following ions hydrolyze in aqueous
written? solution?
3. What is meant by the term buffered solution? a. NO −3 d. K+ g. CO2−
3
4. Which of the following combinations of solutions b. F − e. CH3COO− h. PO 3−

4
would form buffers when they are mixed? c. NH+4 f. SO 2−
4
a. 50 mL of 1.0 M HCl and 50 mL of 1.0 M NaCl 9. Identify the following solutions as acidic, basic,
b. 25 mL of 0.5 M HNO2 and 50 mL of 1.0 M or neutral.
NaNO2 a. 0.5 M KI c. 0.25 M NH4NO3
c. 25 mL of 1.0 M HNO2 and 25 mL of 1.0 M NaCl b. 0.10 M Ba(OH)2 d. 0.05 M K2CO3
5. What is meant by the ion product constant for 10. Identify the acid and base from which each
water? What is the value of this constant? of the following salts was formed.
6. For each of the following reactions, identify each a. K2CrO4 c. CaF2
conjugate acid-base pair. b. Ca(CH3COO)2 d. (NH4)2SO4
a. H CO + H O ←⎯ ⎯→ HCO− + H O+
2 3 2 3 3
⎯→ H O+ + OH− Critical Thinking
b. H2O + H2O ←⎯ 3
⎯→ HS− + NH+ 11. RELATING IDEAS Describe how to make a buffer
c. H2S + NH3 ←⎯ 4 solution using a strong base and one other
⎯→ H PO + OH−
d. H2PO4− + H2O ←⎯ reagent.
3 4
612 CHAPTER 18
Solubility Equilibrium SECTION 4
OBJECTIVES
Explain what is meant by
I onic solids dissolve in water until they are in equilibrium with their solubility product constants,
ions.An equilibrium expression can be written from the balanced chemi- and calculate their values.
cal equation of the solid’s dissociation. Concentrations of the ions can
be determined from the balanced chemical equation and solubility data. Calculate solubilities using
The ion concentrations can then be used to determine the value of the solubility product constants.
equilibrium constant. The numerical value for the equilibrium constant
can be used to predict whether precipitation occurs when solutions of
various concentrations are combined. Carry out calculations to
predict whether precipitates
will form when solutions
are combined.
Solubility Product
A saturated solution contains the maximum amount of solute possible
at a given temperature in equilibrium with an undissolved excess of the
substance. A saturated solution is not necessarily a concentrated solu-
tion. The concentration may be high or low, depending on the solubility
of the solute.
A general rule is often used to express solubilities qualitatively. By
this rule, a substance is said to be soluble if the solubility is greater than
1 g per 100 g of water and slightly soluble if less than that. Even sub-
stances we have previously referred to as “insoluble” are slightly solu-
ble. We will describe the degree of solubility with an equilibrium
constant.
The equilibrium principles developed in this chapter apply to all satu-
rated solutions of slightly soluble salts. Silver chloride is an example of
a slightly soluble salt. Its solution reaches saturation when the Ag+ and
Cl− concentrations are 1.3 × 10−5 M, or about 2 × 10−4 g of AgCl in
100 mL. When mixed, all Ag+ and Cl − ions in excess of this concentra-
tion eventually precipitate as AgCl.
Consider the equilibrium system in a saturated solution of silver
chloride containing an excess of the solid AgCl. This system is repre-
sented by the following equilibrium equation and equilibrium-constant
expression.
AgCl(s) ←⎯ ⎯→ Ag+(aq) + Cl −(aq)
The equation represents a heterogeneous reaction, as described on

page 599. Once again, we follow the convention of writing the equilibri-
um expression without including the solid species. Therefore, [AgCl]
does not appear in the final expression. The resulting equilibrium
expression gives the solubility product constant Ksp. The solubility
product constant of a substance is the product of the molar concentra-
tions of its ions in a saturated solution, each raised to the power that is the
coefficient of that ion in the balanced chemical equation.
Ksp = [Ag+][Cl −]
This equation is the solubility equilibrium expression for the reaction. It

expresses the fact that the solubility product constant, Ksp , of AgCl is the
product of the molar concentrations of its ions in a saturated solution.
Calcium fluoride is another slightly soluble salt. The equilibrium in a
saturated CaF2 solution is described by the following equation.
⎯→ Ca2+(aq) + 2F −(aq)
CaF2(s) ←⎯
The solubility product constant has the following form.
Ksp = [Ca2+][F −]2
Notice that Ksp is the product of the molar concentration of Ca2+ ions
and the molar concentration of F − ions squared, as required by the bal-
anced chemical equilibrium expression.
The numerical value of Ksp can be determined from solubility data.
These data indicate that a maximum of 1.9 × 10−4 g of AgCl can dissolve
in 100. g of water at 25°C. One mole of AgCl has a mass of 143.32 g. The
solubility of AgCl can therefore be expressed in moles per liter of
water, which is very nearly equal to moles per liter of solution.
1.9 × 10−4 g AgCl 1 g H2O 1000 mL 1 mol AgCl

× × ×
100. g H2O 1 mL H2O 1L 143.32 g AgCl
= 1.3 × 10−5 mol/L
Silver chloride dissociates in solution, contributing equal numbers of

Ag+ and Cl − ions. The ion concentrations in the saturated solution are
therefore 1.3 × 10−5 mol/L.
[Ag+] = 1.3 × 10−5

[Cl −] = 1.3 × 10−5
and
Ksp = [Ag+][Cl −]
Ksp = (1.3 × 10−5)(1.3 × 10−5)
Ksp = (1.3 × 10−5)2
Ksp = 1.7 × 10−10
This result is the solubility product constant of AgCl at 25°C.

The solubility of CaF2 is 8.6 × 10−3 g/100 g of water at 25°C. Expressed
in moles per liter, as before, this concentration becomes 1.1 × 10−3
mol/L. CaF2 dissociates in solution to yield twice as many F − ions as
614 CHAPTER 18
Ca2+ ions. The ion concentrations in the saturated solution are 1.1 × 10−3
for the calcium ion and 2(1.1 × 10−3), or 2.2 × 10−3, for the fluoride ion.
Note that at equilibrium at 25°C, [Ca2+] equals the solubility of 1.1 ×
10−3 mol/L but [F −] equals twice the solubility, or 2.2 × 10−3 mol/L. The
number of moles of positive and negative ions per mole of compound
must always be accounted for when using Ksp and solubilities.
Ksp = [Ca2+][F −]2

Ksp = (1.1 × 10−3)(2.2 × 10−3)2
Ksp = 5.3 × 10−9
Thus, the solubility product constant of CaF2 is 5.3 × 10−9 at 25°C.

It is difficult to measure very small concentrations of a solute with
precision. For this reason, solubility data from different sources may
report different values of Ksp for a substance. Thus, calculations of Ksp
ordinarily should be limited to two significant figures. Representative
values of Ksp at 25°C for some slightly soluble compounds are listed in
Table 3. Assume that all data used in Ksp calculations have been taken
at 25°C unless otherwise specified.
At this point, you should note the difference between the solubility of
a given solid and its solubility product constant. Remember that the
solubility product constant is an equilibrium constant representing the
product of the molar concentrations of its ions in a saturated solution. It
TABLE 3 Solubility Product Constants, Ksp , at 25°C

Salt Ion product Ksp Salt Ion product Ksp
AgCH3COO [Ag+][CH −
3COO ] 1.9 × 10−3 CuCl [Cu+][Cl −] 1.2 × 10−6
AgBr [Ag+][Br −] 5.0 × 10−13 CuS [Cu2+][S2−] 6.3 × 10−36
Ag2CO3 [Ag+]2[CO2−
3 ] 8.1 × 10−12 FeS [Fe2+][S2−] 6.3 × 10−18
AgCl [Ag+][Cl −] 1.8 × 10−10 Fe(OH)2 [Fe2+][OH−]2 8.0 × 10−16
AgI [Ag+][I−] 8.3 × 10−17 Fe(OH)3 [Fe3+][OH −]3 4 × 10−38
Ag2S [Ag+]2[S2−] 6.3 × 10−50 HgS [Hg2+][S2−] 1.6 × 10−52
Al(OH)3 [Al3+][OH −]3 1.3 × 10−33 MgCO3 [Mg2+][CO2−
3 ] 3.5 × 10−8
BaCO3 [Ba2+][CO2−
3 ] 5.1 × 10−9 Mg(OH)2 [Mg2+][OH −]2 1.8 × 10−11
BaSO4 [Ba2+][SO2−
4 ] 1.1 × 10−10 MnS [Mn2+][S2−] 2.5 × 10−13
CdS [Cd2+][S2−] 8.0 × 10−27 PbCl2 [Pb2+][Cl −]2 1.6 × 10−5
CaCO3 [Ca2+][CO2−
3 ] 2.8 × 10−9 PbCrO4 [Pb2+][CrO2−
4 ] 2.8 × 10−13
CaF2 [Ca2+][F −]2 5.3 × 10−9 PbSO4 [Pb2+][SO2−
4 ] 1.6 × 10−8
Ca(OH)2 [Ca2+][OH −]2 5.5 × 10−6 PbS [Pb2+][S2−] 8.0 × 10−28
CaSO4 [Ca2+][SO2−
4 ] 9.1 × 10−6 SnS [Sn2+][S2−] 1.0 × 10−25
CoCO3 [Co2+][CO2−
3 ] 1.4 × 10−13 SrSO4 [Sr2+][SO2−
4 ] 3.2 × 10−7
CoS [Co2+][S2−] 4.0 × 10−21 ZnS [Zn2+][S2−] 1.6 × 10−24

has only one value for a given solid at a given temperature. The solubility
of a solid is an equilibrium position that represents the amount of the solid
required to form a saturated solution with a specific amount of solvent. It
has an infinite number of possible values at a given temperature and is
dependent on other conditions, such as the presence of a common ion.
SAMPLE PROBLEM B
Calculate the solubility product constant, Ksp , for copper(I) chloride, CuCl, given that the solubility of
this compound at 25°C is 1.08 10–2 g/100. g H2O.
SOLUTION
1 ANALYZE Given: solubility of CuCl = 1.08 × 10−2 g CuCl/100. g H2O
Unknown: Ksp
2 PLAN Start by converting the solubility of CuCl in g/100. g H2O to mol/L. You will need the molar
mass of CuCl to get moles CuCl from grams CuCl. Then use the solubility of the [Cu+] and
[Cl−] ions in the Ksp expression and solve for Ksp.
g CuCl 1 g H2O 1000 mL 1 mol CuCl

× × × = solubility in mol/L
100. g H2O 1 mL H2O 1L g CuCl
⎯→ Cu+(aq) + Cl −(aq)
CuCl(s) ←⎯
Ksp = [Cu+][Cl −]
[Cu+] = [Cl −] = solubility in mol/L
3 COMPUTE The molar mass of CuCl is 99.0 g/mol.

1.08 × 10−2 g CuCl 1 g H2O 1000 mL 1 mol CuCl
solubility = × × × =
100. g H2O 1 mL 1L 99.0 g CuCl
1.09 × 10−3 mol/L CuCl

[Cu+] = [Cl −] = 1.09 × 10−3 mol/L
Ksp = (1.09 × 10−3)(1.09 × 10−3) = 1.19 × 10−6
4 EVALUATE The answer contains the proper number of significant figures and is close to the Ksp value
given in Table 3.
1. Calculate the solubility product constant, Ksp, of lead(II) chloride,

PbCl2, which has a solubility of 1.0 g/100. g H2O at 20°C. Go to go.hrw.com for
2. A 5.0 gram sample of Ag2SO4 will dissolve in 1.0 L of water. that ask you to calculate
Calculate the solubility product constant for this salt. solubility product
constants.
Keyword: HC6EQUX
616 CHAPTER 18
Calculating Solubilities
Once known, the solubility product constant can be used to determine
the solubility of a slightly soluble salt. Suppose you wish to know how
many moles of barium carbonate, BaCO3, can be dissolved in 1 L of
water at 25°C. From Table 3, Ksp for BaCO3 has the numerical value
5.1 × 10−9. The equilibrium equation is written as follows.
⎯→ Ba2+(aq) + CO2−(aq)
BaCO3(s) ←⎯ 3
Given the value for Ksp, we can write the solubility equilibrium expres-
sion as follows.
Ksp = [Ba2+][CO2− −9
3 ] = 5.1 × 10
Therefore, BaCO3 dissolves until the product of the molar concentra-

−9
tions of Ba2+ ions and CO2− 3 ions equals 5.1 × 10 . The solubility
equilibrium equation shows that Ba ions and CO2−
2+
3 ions enter the
solution in equal numbers as the salt dissolves. Thus, they have the same
concentration. Let [Ba2+] = x. Then [CO2− 3 ] = x also.
−9
3 ] = Ksp = 5.1 × 10
[Ba2+][CO2−
(x)(x) = x2 = 5.1 × 10−9
x = 5.
0−9
1
1×
The molar solubility of BaCO3 is 7.1 × 10−5 mol/L.
Thus, the solution concentration is 7.1 × 10−5 M for Ba2+ ions and
7.1 × 10−5 M for CO2−
3 ions.
SAMPLE PROBLEM C
Calculate the solubility of silver bromide, AgBr, in mol/L, using the Ksp value for this compound listed
in Table 3.
SOLUTION
1 ANALYZE Given: Ksp = 5.0 × 10−13
Unknown: solubility of AgBr
2 PLAN ⎯→ Ag+(aq) + Br−(aq)

AgBr ←⎯
Ksp = [Ag+][Br−]
[Ag+] = [Br−], so let [Ag+] = x and [Br−] = x
3 COMPUTE Ksp = [Ag+][Br−]

Ksp = x2
x2 = 5.0 × 10−13
x = −13
5.0 × 10
Solubility of AgBr =
5.0 × 1− −7
0 13 = 7.1 × 10 mol/L

4 EVALUATE The answer has the proper number of significant figures and is close to an estimated value
of 7.0 × 10−7 calculated as 49
× 10−14
.
1. Calculate the solubility of cadmium sulfide, CdS, in mol/L, given

the Ksp value listed in Table 3.
2. Determine the concentration of strontium ions in a saturated Go to go.hrw.com for
solution of strontium sulfate, SrSO4, if the Ksp for SrSO4 is more practice problems
3.2 × 10−7. that ask you to calculate
solubilities.
Keyword: HC6EQUX
Precipitation Calculations
In an earlier example, BaCO3 served as the source of both Ba2+ and CO2− 3
ions. Because each mole of BaCO3 yields one mole of Ba2+ ions and one
mole of CO2− 3 ions, the concentrations of the two ions were equal.
However, the equilibrium condition does not require that the two ion
concentrations be equal. Equilibrium will still be established so that the
ion product [Ba2+][CO2− 3 ] does not exceed the value of Ksp for the system.
Similarly, if the ion product [Ca2+][F −]2 is less than the value of Ksp
at a particular temperature, the solution is unsaturated. If the ion product
is greater than the value for Ksp, CaF2 precipitates. This precipitation
reduces the concentrations of Ca2+ and F − ions until equilibrium is
established.
Suppose that unequal quantities of BaCl2 and Na2CO3 are dissolved
in water and that the solutions are mixed. If the ion product
[Ba2+][CO2− 3 ] exceeds the Ksp of BaCO3, a precipitate of BaCO3 forms.
After precipitation, the ion concentrations are such that [Ba2+][CO2− 3 ]
equals the Ksp.
Ag+ Pb2+ Ag+
NO3− NO3− CrO2−

4
(a) (b) (c)
FIGURE 13 Nitrate salts of Ag+ (a)

and Pb2+ (b) are soluble. When chro- Pb2+ Ag+ Fe3+
mate ions, CrO42−, combine with Ag+
(c) or Pb2+ (d), a slightly soluble salt
forms. Thiocyanate ions, SCN−, can
form a slightly soluble salt with Ag+
(e) or a soluble salt with Fe3+ (f). CrO2−
4 SCN− SCN−
(d) (e) (f)
618 CHAPTER 18
Substances differ greatly in their tendencies to form precipitates
when mixed in moderate concentrations. The photos in Figure 13 show
the behavior of some anions in the presence of certain cations. Note that
some of the combinations have produced precipitates and some have
not. The solubility product can be used to predict whether a precipitate
forms when two solutions are mixed.
SAMPLE PROBLEM D
Will a precipitate form if 20.0 mL of 0.010 M BaCl2 is mixed with 20.0 mL of 0.0050 M Na2SO4?
SOLUTION
1 ANALYZE Given: concentration of BaCl2 = 0.010 M
volume of BaCl2 = 20.0 mL
concentration of Na2SO4 = 0.0050 M
volume of Na2SO4 = 20.0 mL
Unknown: whether a precipitate forms
2 PLAN The two possible new pairings of ions are NaCl and BaSO4. Of these, only BaSO4 is a
slightly soluble salt. It will precipitate if the ion product [Ba2+][SO2−
4 ] in the mixed solution
exceeds Ksp for BaSO4. From the list of solubility products in Table 3, the Ksp is found
to be 1.1 × 10−10. The solubility equilibrium equation follows.
⎯→ Ba2+(aq) + SO2−(aq)
BaSO4(s) ←⎯ 4
The solubility equilibrium expression is written as follows.

Ksp = [Ba2+][SO2− −10
4 ] = 1.1 × 10
First [Ba2+] and [SO2−

4 ] in the above solution must be found. Then the ion product is
calculated and compared with the Ksp.
3 COMPUTE Calculate the mole quantities of Ba2+ and SO2−

4 ions.
0.010 mol Ba2+
0.020 L × = 0.000 20 mol Ba2+
1L
0.0050 mol SO2−

4
0.020 L × = 0.000 10 mol SO2−
4
1L
Calculate the total volume of solution containing Ba2+ and SO2−
4 ions.
0.020 L + 0.020 L = 0.040 L
Calculate the Ba2+ and SO2−
4 ion concentrations in the combined solution.
0.000 20 mol Ba2+
= 5.0 × 10−3 mol/L Ba2+
0.040 L
0.000 10 mol SO2−

= 2.5 × 10−3 mol/L SO2−
4
4
0.040 L

Calculate the ion product.
−3 −3
4 ] = (5.0 × 10 )(2.5 × 10 )
[Ba2+][SO2−
= 1.2 × 10−5
The ion product, 1.2 × 10−5, is greater than the value of Ksp, 1.1 × 10−10, so precipitation
occurs.
4 EVALUATE The answer contains the appropriate number of significant figures and is close to an esti-
mated value of 1 × 10−5, calculated as (5 × 10−3)(2 × 10−3); because 10−5 > 10−10, precipitation
should occur.
1. Does a precipitate form when 100. mL of 0.0025 M AgNO3

and 150. mL of 0.0020 M NaBr solutions are mixed? Go to go.hrw.com for
2. Does a precipitate form when 20. mL of 0.038 M Pb(NO3)2 that ask you to perform
and 30. mL of 0.018 M KCl solutions are mixed? precipitation
calculations.
Keyword: HC6EQUX
Limitations on the Use of Ksp

The solubility product principle can be very useful when applied to solu-
tions of slightly soluble substances. It cannot be applied to solutions of sol-
uble substances. This is because the positive and negative ions attract each
other, and this attraction becomes appreciable when the ions are close
together. Sometimes it is necessary to consider two equilibria simultane-
ously. For example, if either ion hydrolyzes, the salt will be more soluble
than predicted when only the solubility product constant is used. The solu-
bility product is also sensitive to changes in solution temperature to the
extent that the solubility of the dissolved substance is affected by such
changes. All of these factors limit the conditions under which the solubility
product principle can be applied.
SECTION REVIEW 6. Determine whether a precipitate will form if

1. What is a solubility product constant? How are 20.0 mL of 1.00 × 10−7 M AgNO3 is mixed
such constants determined? with 20.0 mL of 2.00 × 10−9 M NaCl at 25°C.
2. How are solubility product constants used to Critical Thinking
calculate solubilities? 7. ANALYZING DATA A solution is 0.20 M in each of
3. What is an ion product? the following: Ca(NO3)2, Cr(NO3)3, and La(NO3)3.
4. How are calculations to predict possible precipita- Solid NaF is added to the solution until the [F–]
tion carried out? of the solution is 1.0 × 10–4 M. Given the values
of Ksp below, describe what will happen.
5. What is the value of Ksp for Ag2SO4 if 5.40 g CaF2 = 3.9 × 10–11; CrF3 = 6.6 × 10–11; and
is soluble in 1.00 L of water? LaF3 = 4.0 × 10–17
620 CHAPTER 18
CHAPTER HIGHLIGHTS
The Nature of Chemical Equilibrium
Vocabulary • A reaction system in which the forward and reverse reactions
reversible reaction occur simultaneously and at the same rate is said to be at equi-
chemical equilibrium librium. Both reactions continue, but there is no net change in
equilibrium constant the composition of the system.
chemical equilibrium expression • At equilibrium, the ratio of the product of the molar concen-
trations of substances formed to the product of the molar con-
centrations of reactants, each raised to the appropriate power,
has a definite numerical value, K, which is the equilibrium con-
stant at a given temperature.
Shifting Equilibrium
Vocabulary • According to Le Châtelier’s principle, when a stress (a change
common-ion effect in concentration, pressure, or temperature) is applied to a sys-
tem at equilibrium, the equilibrium is shifted in the direction
that relieves the stress.
• The common-ion effect is recognized when a solution contain-
ing ions such as those of a reactant or a product in an equilibri-
um system is added to the system. Le Châtelier’s principle
explains the response of the system to the stress.
Equilibria of Acids, Bases, and Salts

Vocabulary • The equilibrium expression for the ionization constant of the
acid ionization constant weak acid HA follows.
buffered solution [H3O+][A−]
Ka =
hydrolysis [HA]
• Salts formed from strong bases and weak acids produce aque-
ous solutions that are basic because of anion hydrolysis.
• Salts formed from strong acids and weak bases produce aque-
ous solutions that are acidic because of cation hydrolysis.
• Salts formed from strong acids and strong bases do not
hydrolyze in water, and their solutions are neutral.
• Salts formed from weak acids and weak bases may produce
neutral, acidic, or basic solutions, depending on the relative
amounts of cation and anion hydrolysis.
Solubility Equilibrium
Vocabulary • Ions of salts that are slightly soluble form saturated aqueous
solubility product constant solutions at low concentrations. The solubility equilibrium
expression for such salts yields a constant—the solubility product
constant, Ksp.

CHAPTER REVIEW
For more practice, go to the Problem Bank in Appendix D.
at equilibrium, determine the concentration of
The Nature of Chemical N2 at that point.
Equilibrium N2(g) + 3H2(g) ←⎯⎯→ 2NH (g)
3
7. The value of the equilibrium constant for the
SECTION 1 REVIEW reaction below is 40.0 at a specified temperature.
1. Describe and explain how the concentrations of What would be the value of that constant for the
A, B, C, and D change from the time when A reverse reaction under the same conditions?
and B are first combined to the point at which ⎯→ 2HI(g)
H2(g) + I2(g) ←⎯
equilibrium is established for the reaction
A + B ←⎯⎯→ C + D.
2. a. Write the general expression for an equilibri- Shifting Equilibrium
um constant based on the equation nA +
⎯→ xC + yD + . . .
mB + . . . ←⎯
SECTION 2 REVIEW
b. What information is provided by the value of 8. Predict whether each of the following pressure
K for a given equilibrium system at a speci- changes would favor the forward or reverse
fied temperature? reaction.
2NO(g) + O2(g) ←⎯ ⎯→ 2NO (g)
3. In general, which reaction is favored (forward 2
or reverse) if the value of K at a specified tem- a. increased pressure
perature is b. decreased pressure
a. very small? 9. In heterogeneous reaction systems, what types
b. very large? of substances do not appear in the equilibrium
constant expression? Why?
10. Explain the effect of a catalyst on an equilibri-
PRACTICE PROBLEMS
um system.
4. Determine the value of the equilibrium con- 11. Predict the effect of each of the following on
stant for each reaction given, assuming that the the indicated equilibrium system in terms of the
equilibrium concentrations are found to be direction of equilibrium shift (forward, reverse,
those specified. (Concentrations are in mol/L.) or neither).
(Hint: See Sample Problem A.) ⎯→ 2HCl(g) + 184 kJ
H2(g) + Cl2(g) ←⎯
a. A + B ←⎯⎯→ C; [A] = 2.0; [B] = 3.0; [C] = 4.0
a. addition of Cl2
b. D + 2E ←⎯⎯→ F + 3G; [D] = 1.5; [E] = 2.0;
b. removal of HCl
[F] = 1.8; [G] = 1.2 c. increased pressure
c. N2(g) + 3H2(g) ←⎯ ⎯→ 2NH (g); [N ] = 0.45;
3 2 d. decreased temperature
[H2] = 0.14; [NH3] = 0.62 e. removal of H2
5. An equilibrium mixture at a specific tempera- f. decreased pressure
ture is found to consist of 1.2 × 10−3 mol/L HCl, g. addition of a catalyst
3.8 × 10−4 mol/L O2, 5.8 × 10−2 mol/L H2O, and h. increased temperature
5.8 × 10−2 mol/L Cl2 according to the following: i. decreased system volume
4HCl(g) + O2(g) ←⎯ ⎯→ 2H O(g) + 2Cl (g).
2 2 12. How would the changes in (a) through (i) of
Determine the value of the equilibrium con- item 11 affect the new equilibrium concentra-
stant for this system. tion of HCl and the value of K at the new
6. At 450°C, the value of the equilibrium constant equilibrium?
for the following system is 6.59 × 10−3. If 13. Explain why changes in the concentrations of the
[NH3] = 1.23 × 10−4 M and [H2] = 2.75 × 10−2 M reactants and products at equilibrium have no
impact on the value of the equilibrium constant.
622 CHAPTER 18
CHAPTER REVIEW
14. What relative pressure (high or low) would 21. Explain why the pH of a solution containing
result in the production of the maximum level both acetic acid and sodium acetate is higher
of CO2 according to the following equation? than that of a solution containing the same con-
Why? centration of acetic acid alone.
⎯→ 2CO (g)
2CO(g) + O2(g) ←⎯ 22. The ionization constant, Ka , for acetic acid is
2
15. What relative conditions (reactant concentra- 1.8 × 10−5 at 25°C. Explain the significance of
tions, pressure, and temperature) would favor a this value.
high equilibrium concentration of the under- 23. a. From the development of Ka described in
lined substance in each of the following equilib- Section 3, show how you would express an ion-
rium systems? ization constant, Kb, for the weak base NH3.
a. 2CO(g) + O2(g) ←⎯ ⎯→ 2CO (g) + 167 kJ b. In this case, Kb = 1.8 × 10−5. What is the signifi-
2
b. Cu2+(aq) + 4NH (aq) ←⎯ ⎯→ cance of this numerical value to equilibrium?
3
4 (aq) + 42 kJ
Cu(NH3)2+
⎯→ H (g) + I (g)
c. 2HI(g) + 12.6 kJ ←⎯ 2 2 Solubility Equilibrium
⎯→
d. 4HCl(g) + O (g) ←⎯
2
SECTION 4 REVIEW
2H2O(g) + 2Cl2(g) + 113 kJ
⎯→ PCl (g) + Cl (g) 24. Explain why a saturated solution is not neces-
e. PCl5(g) + 88 kJ ←⎯ 3 2 sarily a concentrated solution.
16. The reaction between hemoglobin, Hb, and oxy- 25. What rule of thumb is used to distinguish
gen, O2, in red blood cells is responsible for between soluble and slightly soluble
transporting O2 to body tissues. This process can substances?
be represented by the following equilibrium 26. What is the relative ion concentration of an
reaction: ionic substance typically involved in solubility
Hb(aq) + O2(g) ←⎯ ⎯→ HbO (aq) equilibrium systems?
2
What will happen to the concentration of oxy- 27. What is the relationship between Ksp and the
genated hemoglobin, HbO2, at high altitude, product of the ion concentrations in terms of
where the pressure of oxygen is 0.1 atm instead determining whether a solution of those ions
of 0.2 atm, as it is at sea level? is saturated?
17. What two factors determine the extent to which
reacting ions are removed from solution?
PRACTICE PROBLEMS
18. Identify the three conditions under which ionic
reactions can run to completion, and write an 28. The ionic substance EJ dissociates to form
equation for each. E2+ and J2− ions. The solubility of EJ is 8.45 ×
10−6 mol/L. What is the value of the solubility
product constant? (Hint: See Sample Problem B.)
29. Calculate the solubility product constant Ksp for
Equilibria of Acids, Bases, each of the following, based on the solubility
and Salts information provided:
a. BaSO4 = 2.4 × 10−4 g/100. g H2O at 20°C
SECTION 3 REVIEW
b. Ca(OH)2 = 0.173 g/100. g H2O at 20°C
19. a. Write the ion product constant expression 30. Calculate the molar solubility of a substance
for water. MN that ionizes to form M2+ and N2− ions,
b. What is the value of this constant at 25°C? given that Ksp = 8.1 × 10−6. (Hint: See Sample
20. List and distinguish between the four general Problem C.)
categories of salts, based on their hydrolysis
properties, and give an example of each.

CHAPTER REVIEW
31. Use the Ksp values given in Table 3 to evaluate 40. Calculate the equilibrium constant, K, for the
the solubility of each of the following in moles following reaction at 900°C.
per liter. H2(g) + CO2(g) ←⎯ ⎯→ H O(g) + CO(g)
2
a. AgBr The components were analyzed, and it was found
b. CoS that [H2] = 0.061 mol/L, [CO2] = 0.16 mol/L,
32. Complete each of the following relative to [H2O] = 0.11 mol/L, and [CO] = 0.14 mol/L.
the reaction that occurs when 25.0 mL of 41. A solution in equilibrium with solid barium
0.0500 M Pb(NO3)2 is combined with 25.0 mL phosphate is found to have a barium ion concen-
of 0.0400 M Na2SO4 if equilibrium is reached tration of 5.0 × 10−4 M and a Ksp of 3.4 × 10−23.
at 25°C. Calculate the concentration of phosphate ion.
a. Write the solubility equilibrium equation at 42. At 25°C, the value of K is 1.7 × 10−13 for the fol-
25°C. lowing reaction.
b. Write the solubility equilibrium expression 2N2O(g) + O2(g) ←⎯ ⎯→ 4NO(g)
for the net reaction. It is determined that [N2O] = 0.0035 mol/L and
33. The ionic substance T3U2 ionizes to form T2+ [O2] = 0.0027 mol/L. Using this information, what
and U3− ions. The solubility of T3U2 is 3.8 × is the concentration of NO(g) at equilibrium?
10−10 mol/L. What is the value of the solubility 43. Tooth enamel is composed of the mineral
product constant? hydroxyapatite, Ca5(PO4)3OH, which has a Ksp
34. A solution of AgI contains 2.7 × 10−10 mol/L Ag+. of 6.8 × 10−37. The molar solubility of hydroxy-
What is the maximum I− concentration that can apatite is 2.7 × 10−5 mol/L. When hydroxyap-
exist in this solution? atite is reacted with fluoride, the OH− is
35. Calculate whether a precipitate will form if replaced with the F− ion on the mineral, form-
0.35 L of 0.0044 M Ca(NO3)2 and 0.17 L of ing fluorapatite, Ca5(PO4)3F. (The latter is hard-
0.000 39 M NaOH are mixed at 25°C. (See Table 3 er and less susceptible to cavities.) The Ksp of
for Ksp values.) (Hint: See Sample Problem D.) fluorapatite is 1 × 10−60. Calculate the molar sol-
36. Determine whether a precipitate will form if ubility of fluorapatite in water. Given your cal-
1.70 g of solid AgNO3 and 14.5 g of solid NaCl culations, can you support the fluoridation of
are dissolved in 200. mL of water to form a drinking water?
solution at 25°C. 44. Determine if a precipitate will form when
37. If 2.50 × 10−2 g of solid Fe(NO3)3 is added to 0.96 g Na2CO3 is combined with 0.20 g BaBr2
100. mL of a 1.0 × 10−4 M NaOH solution, will a in a 10. L solution (Ksp = 2.8 × 10−9).
precipitate form? 45. For the formation of ammonia, the equilibrium
constant is calculated to be 5.2 × 10−5 at 25°C.
After analysis, it is determined that [N2] = 2.00 M
MIXED REVIEW and [H2] = 0.80 M. How many grams of ammonia
are in the 10. L reaction vessel at equilibrium?
38. Calcium carbonate is only slightly soluble in Use the following equilibrium equation.
water. N2(g) + 3H2(g) ←⎯⎯→ 2NH (g)
3
a. Write the equilibrium equation for calcium
carbonate in solution.
b. Write the solubility product constant expres- CRITICAL THINKING
sion, Ksp, for the equilibrium in a saturated
solution of CaCO3. 46. Relating Ideas Let s equal the solubility, in
39. Calculate the concentration of Hg2+ ions in a mol/L, of AB2. In terms of s, what is the molar
saturated solution of HgS(s). How many Hg2+ concentration of A? of B? What is the Ksp of
ions are in 1000 L of the solution? AB2?
624 CHAPTER 18
CHAPTER REVIEW
47. Predicting Outcomes When gasoline burns in 51. Carry out library research on the use of cata-
an automobile engine, nitric oxide is formed lysts in industrial processes. Explain what types
from oxygen and nitrogen. Nitric oxide is a of catalysts are used for specific processes, such
major air pollutant. High temperatures such as as the Haber process.
those found in a combustion engine are needed
for the following reaction:
⎯→ 2NO(g)
N2(g) + O2(g) ←⎯ ALTERNATIVE ASSESSMENT
K for the reaction is 0.01 at 2000°C. If 4.0 mol
of N2, 0.1 mol of O2, and 0.08 mol of NO are 52. Research nitrogen narcosis in the library. What
placed in a 1.0 L vessel at 2000°C, predict which causes nitrogen narcosis, and how does it relate
reaction will be favored. to Le Châtelier’s principle?
USING THE HANDBOOK

Graphing Calculator Chemical
48. An equilibrium system helps maintain the pH
Equilibrium
of the blood. Review the material on the carbon
Go to go.hrw.com for a graphing calculator
dioxide–bicarbonate ion equilibrium system in
exercise that asks you to calculate the per-
Group 14 of the Elements Handbook, and
cent ionization for an acid equilibrium.
answer the following.
a. Write the equation for the equilibrium Keyword: HC6EQUX
system that responds to changes in H3O+
concentration.
b. Use Le Châtelier’s principle to explain how
hyperventilation affects this system.
c. How does this system maintain pH when
acid is added?
49. The reactions used to confirm the presence of
transition metal ions often involve the formation
of precipitates. Review the analytical tests for the
transition metals in the Elements Handbook. Use
that information and Table 3 to determine the
minimum concentration of Zn2+ needed to pro-
duce a precipitate that confirms the presence of
Zn. Assume enough sulfide ion reagent is added
to the unknown solution in the test tube to pro-
duce a sulfide ion concentration of 1.4 × 10−20 M.
RESEARCH & WRITING

50. Find photos of several examples of stalagmites
and stalactites in various caves. Investigate the
equilibrium processes involved in the formation
of stalagmites and stalactites.

Math Tutor DETERMINING EQUILIBRIUM CONSTANTS
For a given temperature, you can write a mathematical equation that describes the equi-
librium of a reaction in terms of concentration. The equation defines an equilibrium con-
stant, K, as a function of the concentrations of products and reactants at equilibrium.
Consider an equilibrium process in which reactants A and B form products C and D.
nA + mB ←⎯ ⎯→ xC + yD
The terms n, m, x, and y are the coefficients of the balanced equation.

[C]x[D]y
K= ⎯
[A]n[B]m
Problem-Solving S
• Always use a balanced chemical equation to write an equilibrium-constant equation.
• To write an equation, place the product concentrations in the numerator and the
reactant concentrations in the denominator. Raise each substance’s concentration
to the power equal to the substance’s coefficient in the balanced chemical equation.
• The concentration of any solid or pure liquid that takes part in the reaction is left
out because these concentrations never change.
SAMPLE
Write an equation for the equilibrium constant of the reaction in which nitrogen monoxide
changes to dinitrogen monoxide and nitrogen dioxide.
To write an equation for an equilibrium constant, you must start with a balanced chemical
equation for the equilibrium reaction. By writing the formulas of the compounds mentioned in
the description, you get the unbalanced equilibrium equation NO(g) ←⎯ ⎯→ N O(g) + NO (g).
2 2
Balancing the equation requires a coefficient of 3 in front of NO, giving 3NO(g) ←⎯ ⎯→
N2O(g) + NO2(g). Next, write an equilibrium equation. Remember, each concentration in the
equilibrium equation is raised to a power equal to its coefficient in the balanced chemical equa-
tion.The product concentrations, [N2O] and [NO2], are placed in the numerator.The coefficient
of each of the products is 1, so the exponent of each concentration is 1. There is only one reac-
tant, so its concentration, [NO], is written in the denominator. Its coefficient is 3 in the balanced
chemical equation, so the concentration of NO is raised to the third power.The exponents with
a value of 1 do not have to be written. The resulting equation is
[N2O]1[NO2]1 [N2O][NO2]
K = ⎯⎯ = ⎯⎯
[NO]3 [NO]3
PRACTICE PROBLEMS
1. Write equations for the equilibrium constant of 2. Use the equilibrium concentrations below to cal-
each of the following hypothetical reactions: culate the equilibrium constant for the following
a. A(aq) + 2B(aq) ←⎯⎯→ AB (aq) decomposition reaction:
2
b. 2DE2(g) ←⎯⎯→ D (g) + 2E (g) 2BrF5(g) ←⎯⎯→ Br (g) + 5F (g)
2 2 2 2
[BrF5] = 0.000137 mol/L, [Br2] = 0.00050 mol/L,
and [F2] = 0.0025 mol/L
626 CHAPTER 18
Answer the following items on a separate piece of paper. 7. Le Châtelier’s principle states that
MULTIPLE CHOICE A. at equilibrium, the forward and reverse reac-
tion rates are equal.
1. A chemical reaction is in equilibrium when
B. stresses include changes in concentrations,
A. forward and reverse reactions have ceased.
pressure, and temperature.
B. the equilibrium constant equals 1.
C. to relieve stress, solids and solvents are omit-
C. forward and reverse reaction rates are equal.
ted from equilibrium constant expressions.
D. No reactants remain.
D. chemical equilibria respond to reduce
2. Which change can cause the value of the equi- applied stress.
librium constant to change?
SHORT ANSWER
A. temperature
B. concentration of a reactant 8. Describe the conditions that would allow you to
C. concentration of a product conclusively determine that a solution is satu-
D. None of the above rated. You can use only visual observation and
cannot add anything to the solution.
3. Consider the following reaction:
⎯→ 2CO(g)
2C(s) + O2(g) ←⎯ 9. The graph below shows the neutralization curve
The equilibrium constant expression for this for 100 mL of 0.100 M acid with 0.100 M base.
reaction is Which letter represents the equivalence point?
What type of acid and base produced this
[CO]2 2[CO]
A. ⎯ . C. ⎯ . curve?
[O2] [O2][2C]
[CO]2 [CO]
B. ⎯2 . D. ⎯2 .
[O2][C] [O2] 13
4. The solubility product of cadmium carbonate, 11 d

CdCO3, is 1.0 × 10−12. In a saturated solution of
this salt, the concentration of Cd2+(aq) ions is 9 c
A. 5.0 × 10−13 mol/L. C. 1.0 × 10−6 mol/L. 7
B. 1.0 × 10−12 mol/L. D. 5.0 × 10−7 mol/L.
pH
b
5
5. Consider the following equation for an equilib- a
rium system: 3
2PbS(s) + 3O2(g) + C(s) ←⎯⎯→
2Pb(s) + CO2(g) + 2SO2(g) 1
Which concentration(s) would be included in 0
0 10 30 50 70 90 110 130 150
the denominator of the equilibrium constant
mL base added
expression?
A. Pb(s), CO2(g), and SO2(g)
B. PbS(s), O2(g), and C(s)
EXTENDED RESPONSE
C. O2(g), Pb(s), CO2(g), and SO2(g)
D. O2(g) 10. Explain how the same buffer can resist a change
in pH when either an acid or a base is added.
6. If an exothermic reaction has reached equilib-
Give an example.
rium, then increasing the temperature will
A. favor the forward reaction.
B. favor the reverse reaction.
Keeping a positive attitude dur-
C. favor both the forward and reverse reactions.
ing any test will help you focus on the test and likely
D. have no effect on the equilibrium. improve your score.

MICRO
CHAPTER LAB L A B
Measuring Ka for Acetic Acid

• Compare the conductivities of solutions The acid dissociation constant, Ka, is a measure
of known and unknown hydronium ion of the strength of an acid. Strong acids are complete-
concentrations. ly ionized in water. Because weak acids are only
• Relate conductivity to the concentration partly ionized, they have a characteristic Ka value.
of ions in solution. Properties that depend on the ability of a substance
to ionize, such as conductivity and colligative proper-
• Explain the validity of the procedure ties, can be used to measure Ka. In this experiment,
on the basis of the definitions of strong you will compare the conductivity of a 1.0 M solu-
and weak acids.
tion of acetic acid, CH3COOH, a weak acid, with the
• Compute the numerical value of Ka for conductivities of solutions of varying concentrations
acetic acid. of hydrochloric acid, HCl, a strong acid. From the
comparisons you make, you will be able to estimate
MATERIALS the concentration of hydronium ions in the acetic
• 1.0 M acetic acid, CH3COOH acid solution and calculate its Ka.
• 1.0 M hydrochloric acid, HCl SAFETY

• 24-well plate
• distilled or deionized water
• LED conductivity testers
For review of safety, please see Safety in the
• paper towels Chemistry Laboratory in the front of your book.
• thin-stemmed pipets
PREPARATION
1. Create a table with two columns for recording
your observations. Head the first column “HCl
concentration.” A wide second column can be
headed “Observations and comparisons.”
PROCEDURE
Film canister LED
cap
1. Obtain samples of 1.0 M HCl solution and 1.0 M
20 cm CH3COOH solution.
wire
10 cm 2. Place 20 drops of HCl in one well of a 24-well
wire plate. Place 20 drops of CH3COOH in an adja-
cent well. Label the location of each sample.
Film
canister 3. Test the HCl and CH3COOH with the conduc-
tivity tester. Note the relative intensity of the
Teacher-made LED conductivity tester
628 CHAPTER 18
tester light for each solution. After testing, rinse CLEANUP AND DISPOSAL
the tester probes with distilled water. Remove 9. Clean your lab station. Clean all equip-
any excess moisture with a paper towel. ment, and return it to its proper place.
4. Place 18 drops of distilled water in each of six Dispose of chemicals and solutions in
wells in your 24-well plate. Add 2 drops of containers designated by your teacher. Do not
1.0 M HCl to the first well to make a total of pour any chemicals down the drain or throw any-
20 drops of solution. Mix the contents of this thing in the trash unless your teacher directs you
well thoroughly by picking the contents up in a to do so. Wash your hands thoroughly after all
pipet and returning them to the well. work is finished and before you leave the lab.
5. Repeat this procedure by taking 2 drops of the ANALYSIS AND INTERPRETATION

previous dilution and placing it in the next well
1. Resolving Discrepancies: How did the conduc-
containing 18 drops of water. Return any unused
tivity of the 1.0 M HCl solution compare with
solution in the pipet to the well from which it
that of the 1.0 M CH3COOH solution? Why do
was taken. Mix the new solution with a new
you think this was so?
pipet. (You now have 1.0 M HCl in the well from
Procedure step 2, 0.10 M HCl in the first dilution 2. Organizing Data: What is the H3O+ concentra-
well, and 0.010 M HCl in the second dilution.) tion of the HCl solution that most closely
matched the conductivity of the acetic acid?
6. Continue diluting in this manner until you have
six successive dilutions. The [H3O+] should now 3. Drawing Conclusions: What was the H3O+
range from 1.0 M to 1.0 × 10−6 M. Write the con- concentration of the 1.0 M CH3COOH
centrations in the first column of your data table. solution? Why?
7. Using the conductivity tester, test the cells con-
CONCLUSIONS
taining HCl in order from most concentrated to
least concentrated. Note the brightness of the 1. Applying Models: The acid ionization expression
tester bulb, and compare it with the brightness of for CH3COOH is the following:
the bulb when it was placed in the acetic acid [H3O+][CH3COO−]
Ka =
solution. (Retest the acetic acid well any time for [CH3COOH]
comparison.) After each test, rinse the tester
Use your answer to Analysis and Interpretation
probes with distilled water, and use a paper towel
item 3 to calculate Ka for the acetic acid solution.
to remove any excess moisture. When the bright-
ness produced by one of the HCl solutions is 2. Applying Models: Explain how it is possible
about the same as that produced by the acetic for solutions of HCl and CH3COOH to show
acid, you can infer that the two solutions have the same conductivity but have different
about the same hydronium ion concentration and concentrations.
that the pH of the HCl solution is equal to the
pH of the acetic acid. If the glow from the bulb is EXTENSIONS
too faint to see, turn off the lights or build a light 1. Evaluating Methods: Compare the Ka value
shield around your conductivity tester bulb. that you calculated with the value found on
8. Record the results of your observations by noting page 606 of your text. Calculate the percent
which HCl concentration causes the intensity of error for this experiment.
the bulb to most closely match that of the bulb 2. Predicting Outcomes: Lactic acid
when it is in acetic acid. (Hint: If the conductivity (HOOCCHOHCH3) has a Ka of 1.4 × 10−4. Predict
of no single HCl concentration matches that of whether a solution of lactic acid would cause the
the acetic acid, then estimate the value between conductivity tester to glow brighter or dimmer than
the two concentrations that match the best.) a solution of acetic acid with the same concentra-
tion. How noticeable would the difference be?
CHAPTER 19
Oxidation-Reduction
Reactions
Copper oxidizes in air to form the
green patina you see on this building.
Columbus Tower, San Francisco

Oxidation and SECTION 1
Reduction OBJECTIVES
Assign oxidation numbers to
reactant and product species.
Define oxidation and

O xidation-reduction reactions involve a transfer of electrons. Oxida- reduction.
tion involves the loss of electrons, whereas reduction involves the gain
of electrons. Reduction and oxidation half-reactions must occur simul-
taneously. These processes can be identified through the understanding Explain what an oxidation-
and use of oxidation numbers (oxidation states). reduction reaction (redox
reaction) is.
Oxidation States
Oxidation states were defined in Chapter 7. The oxidation number
assigned to an element in a molecule is based on the distribution of elec-
trons in that molecule.The rules by which oxidation numbers are assigned
were given in Chapter 7. These rules are summarized in Table 1.
TABLE 1 Rules for Assigning Oxidation Numbers

Rule Example
1. The oxidation number of any pure element is 0. The oxidation number of Na(s) is 0.
2. The oxidation number of a monatomic ion equals the The oxidation number of
charge on the ion. Cl − is −1.
3. The more electronegative element in a binary compound is assigned The oxidation number
the number equal to the charge it would have if it were an ion. of O in NO is −2.
4. The oxidation number of fluorine in a compound is always −1. The oxidation number of
F in LiF is −1.
5. Oxygen has an oxidation number of −2 unless it is combined with F, The oxidation number
in which it is +1 or +2, or it is in a peroxide, in which it is −1. of O in NO2 is −2.
6. Hydrogen’s oxidation state in most of its compounds is +1 The oxidation number
unless it is combined with a metal, in which case it is −1. of H in LiH is −1.
7. In compounds, Group 1 and 2 elements and aluminum have The oxidation number
oxidation numbers of +1, +2, and +3, respectively. of Ca in CaCO3 is +2.
8. The sum of the oxidation numbers of all atoms The oxidation number of
in a neutral compound is 0. C in CaCO3 is +4.
9. The sum of the oxidation numbers of all atoms in a The oxidation number of
polyatomic ion equals the charge of the ion. P in H2PO−4 is +5.
OXIDATION-REDUCTION REACTIONS 631

FIGURE 1 The color of solutions
containing chromium compounds
changes with the oxidation state of
chromium.
+2 +3 +6 +6
Oxidation state
Chromium provides a very visual example of oxidation numbers.

Different oxidation states of chromium have dramatically different col-
ors, as can be seen in Figure 1. Solutions with the same oxidation state
show less dramatic differences. The chromium(II) chloride solution is
blue, chromium(III) chloride solution is green, potassium chromate
solution is yellow, and potassium dichromate solution is orange.
Oxidation
Processes in which the atoms or ions of an element experience an
increase in oxidation state are oxidation processes. The combustion of
metallic sodium in an atmosphere of chlorine gas is shown in Figure 2.
The sodium ions and chloride ions produced during this strongly
exothermic reaction form a cubic crystal lattice in which sodium cations
are ionically bonded to chloride anions. The chemical equation for this
reaction is written as follows.
2Na(s) + Cl2(g) ⎯→ 2NaCl(s)
The formation of sodium ions illustrates an oxidation process because

each sodium atom loses an electron to become a sodium ion. The oxi-
dation state is represented by placing an oxidation number above the
symbol of the atom and the ion.
0 +1
Na ⎯→ Na+ + e−
FIGURE 2 Sodium and chlorine
react violently to form NaCl. The The oxidation state of sodium has changed from 0, its elemental
synthesis of NaCl from its elements state, to the +1 state of the ion (Rules 1 and 7, Table 1). A species whose
illustrates the oxidation-reduction oxidation number increases is oxidized. The sodium atom is oxidized to
process. a sodium ion.
632 CHAPTER 19
Reduction
Processes in which the oxidation state of an element decreases are reduc-
tion processes. Consider the behavior of chlorine in its reaction with
sodium. Each chlorine atom accepts an electron and becomes a chloride
ion. The oxidation state of chlorine decreases from 0 to −1 for the chlo-
ride ion (Rules 1 and 2, Table 1).
0 −1
Cl2 + 2e− ⎯→ 2Cl−
A species that undergoes a decrease in oxidation state is reduced. The

chlorine atom is reduced to the chloride ion.
Oxidation and Reduction as a Process FIGURE 3 Copper is oxidized and

nitrogen dioxide is produced when
this penny is placed in a concentrat-
Electrons are released in oxidation and acquired in reduction. There-
ed nitric acid solution.
fore, for oxidation to occur during a chemical reaction, reduction must
also occur. Furthermore, the number of electrons produced in oxidation
must equal the number of electrons acquired in reduction. This makes
sense when you recall that electrons are negatively charged and that for
charge to be conserved, the number of electrons lost must equal the
number of electrons gained. You learned in Chapter 8 that mass is con-
served in any chemical reaction. Therefore, the masses of the elements
that undergo oxidation and reduction and the electrons that are
exchanged are conserved.
A transfer of electrons causes changes in the oxidation states of one or
more elements. Any chemical process in which elements undergo changes www.scilinks.org
in oxidation number is an oxidation-reduction reaction. This name is Topic: Redox Reactions
often shortened to redox reaction. An example of a redox reaction can be Code: HC61281
seen in Figure 3, in which copper is being oxidized and NO3− from nitric
acid is being reduced. The part of the reaction involving oxidation or
reduction alone can be written as a half-reaction. The overall equation for
a redox reaction is the sum of two half-reactions. Because the number of
electrons involved is the same for oxidation and reduction, they cancel
each other out and do not appear in the overall chemical equation.
Equations for the reaction between nitric acid and copper illustrate the
relationship between half-reactions and the overall redox reaction.
0 +2
3Cu ⎯→ Cu2+ + 2e− (oxidation half-reaction)
+5 −2 +1 +4 −2 +1 −2
2NO3− + 2e− + 4H+ ⎯→ 2NO2 + 2H2O (reduction half-reaction)
0 +5 +2 +4
3Cu + 2NO3− + 4H+ ⎯→ Cu2+ + 2NO2 + 2H2O (redox reaction)
Notice that electrons lost in oxidation appear on the product side of

the oxidation half-reaction. Electrons are gained in reduction and

appear as reactants in the reduction half-reaction. When metallic copper
reacts in nitric acid, one copper atom is oxidized to Cu2+ as two nitro-
Photochromic Lenses gen atoms are reduced from a +5 oxidation state to a +4 oxidation state.
Photochromic eyeglasses darken when Atoms are conserved. This is illustrated by the balanced chemical equa-
exposed to ultraviolet light and become tion for the reaction between copper and nitric acid.
transparent again in the absence of If none of the atoms in a reaction change oxidation state, the reaction
ultraviolet light. This process is the result is not a redox reaction. For example, sulfur dioxide gas, SO2, dissolves in
of oxidation-reduction reactions. Silver
water to form an acidic solution containing a low concentration of sul-
chloride and copper(I) chloride are
embedded in the lenses. The chloride furous acid, H2SO3.
ions absorb photons, and the silver chlo- +4 −2 +1 −2 +1 +4 −2
ride dissociates and forms chlorine SO2 + H2O ⎯→ H2SO3
atoms and silver atoms. The elemental
silver darkens the lenses. Note that the
The oxidation states of all elemental species remain unchanged in this
chlorine ions are oxidized and the silver
atoms are reduced. Then, the copper(I) composition reaction. Therefore, it is not a redox reaction.
ions reduce the chlorine atoms and When a solution of sodium chloride is added to a solution of silver
form copper(II) ions. In the reverse nitrate, an ion-exchange reaction occurs and white silver chloride
process, the copper(II) ions oxidize precipitates.
the silver atoms back to the transpar-
+1 −1 +1 +5 −2 +1 +5 −2 +1 −1
ent silver ions.
Na+ + Cl − + Ag+ + NO −3 ⎯→ Na+ + NO −3 + AgCl
The oxidation state of each monatomic ion remains unchanged. Again,

this reaction is not an oxidation-reduction reaction.
Redox Reactions and Covalent Bonds

Both the synthesis of NaCl from its elements and the reaction between
copper and nitric acid involve ionic bonding. Substances with covalent
bonds also undergo redox reactions. An oxidation number, unlike an
ionic charge, has no physical meaning. That is, the oxidation number
assigned to a particular atom is based on its electronegativity relative to
the other atoms to which it is bonded in a given molecule; it is not based
on any real charge on the atom. For example, an ionic charge of 1−
results from the complete gain of one electron by an atom or other neu-
tral species, whereas an oxidation state of −1 means an increased attrac-
tion for a bonding electron. A change in oxidation number does not
require a change in actual charge.
When hydrogen burns in chlorine, a covalent bond forms from the
sharing of two electrons. The two bonding electrons in the hydrogen
chloride molecule are not shared equally. Rather, the pair of electrons
is more strongly attracted to the chlorine atom because of its higher
electronegativity.
0 0 +1 −1
H2 + Cl2 ⎯→ 2HCl
As specified by Rule 3 in Table 1, chlorine in HCl is assigned an oxida-

tion number of −1. Thus, the oxidation number for the chlorine atoms
changes from 0, its oxidation number in the elemental state, to −1; chlo-
rine atoms are reduced. As specified by Rule 1, the oxidation number of
each hydrogen atom in the hydrogen molecule is 0. As specified by Rule
6, the oxidation state of the hydrogen atom in the HCl molecule is +1; the
634 CHAPTER 19
hydrogen atom is oxidized. Neither atom has totally lost or totally gained
any electrons. Hydrogen has donated a share of its bonding electron to
the chlorine but has not completely transferred that electron. The assign-
ment of oxidation numbers allows an approximation of the electron dis-
tribution of a molecule.An element can have different oxidation numbers
in different compounds. This difference in oxidation numbers can reveal
the difference in electron distribution of the compounds.
Reactants and products in redox reactions are not limited to monatom-
ic ions and uncombined elements. Elements in molecular compounds or
polyatomic ions can also be oxidized and reduced if they have more than
one nonzero oxidation state.An example of this is provided in the reaction
between the copper penny and nitric acid in which the nitrate ion, NO3−, is
converted to nitrogen dioxide, NO2. Nitrogen is reduced in this reaction.
Usually, we refer to the oxidation or reduction of the entire molecule or
ion. Instead of saying that the nitrogen atom is reduced, we say the nitrate
ion is reduced to nitrogen dioxide.
+5 +4
. . . + NO3− ⎯→ NO2 + . . .
SECTION REVIEW c. NaOH(aq ) + HCl(aq) ⎯→ NaCl(aq ) + H2O(l)

1. How are oxidation numbers assigned? d. H2(g ) + Cl2(g ) ⎯→ 2HCl(g )
2. Label each of the following half-reactions as either e. SO3(g ) + H2O(l) ⎯→ H2SO4(aq )
an oxidation or a reduction half-reaction: 4. For each redox equation identified in the previous
0 −1 question, determine which element is oxidized and
a. Br2 + 2e − ⎯→ 2 Br − which is reduced.
0 +1
b. Na ⎯→ Na+ + e − Critical Thinking
−1 0 5. ANALYZING INFORMATION Use the following
c. 2 Cl − ⎯→ Cl2 + 2e − equations for the redox reaction between Al3+ and
0 −1 Na to answer the questions below.
d. Cl2 + 2e − ⎯→ 2 Cl − 0 +1
+1 0 3 Na ⎯→ 3 Na+ + 3e − (oxidation)
e. Na+ + e − ⎯→ Na +3 0
0 +2 Al3+ + 3e − ⎯→ Al (reduction)
f. Fe ⎯→ Fe2+ + 2e − 0 +3 +1 0
+2 0 3 Na + Al3+ ⎯→ 3 Na+ + Al (redox reaction)
g. Cu2+ + 2e − ⎯→ Cu
+3 +2 a. Explain how this reaction illustrates that charge
h. Fe3+ + e − ⎯→ Fe2+ is conserved in a redox reaction.
b. Explain how this reaction illustrates that mass
3. Which of the following equations represent redox is conserved in a redox reaction.
reactions?
a. 2KNO3(s ) ⎯→ 2KNO2(s ) + O2(g ) c. Explain why electrons do not appear as react-
ants or products in the combined equation.
b. H2(g) + CuO(s) ⎯→ Cu(s) + H2O(l )

Skunk-Spray Remedy
Have you ever given your pet a sulfur-containing compound that is
tomato juice bath to get rid of the in skunk spray.
smell of skunk spray on its coat?
RSH + 3H2O2 + NaHCO3 ⎯→
Chemistry has a much better way of
RSO3Na + 4H2O + CO2
conquering skunk spray.
Paul Krebaum, the inventor of a The pet should be thoroughly
new “deskunking” formula, says washed with the mixture, and care
that while working as a materials should be taken to avoid the eyes. If
engineer, he constantly had to deal the mixture is left on for a few min-
with the less-than-pleasant smell of utes—long enough for the reaction
the hydrogen sulfide gas that was to occur—and then rinsed away with
released from one of his experi- tap water, the smell will disappear.
ments. Venting off the gas only par- The formula does not bleach or
tially solved the problem. A better cause any other negative side
solution would be to eliminate the effects. Mr. Krebaum does have one
smell entirely. Skunk spray gets its odor from chemi- warning: Mix the formula just before
cals called mercaptans.
Mr. Krebaum rifled through his old using it, because the mixture breaks
chemistry books and found that down quickly. The reaction releases
Because the odor in a skunk’s spray
hydrogen peroxide could oxidize oxygen, so the formula should not
also comes from compounds con-
these sulfur-containing compounds be kept in a sealed container.
taining sulfur in a low oxidation
to much less smelly components. He Pressure will build up, and the lid
state, Mr. Krebaum thought his
immediately whipped up a hydrogen could eventually blow off. For this
solution might also work on this
peroxide mixture, and it worked like reason, bottles of “Krebaum’s
age-old problem. He mixed up a
a charm. Skunkinator” will not be appearing
milder version to try out on the
The equation below shows that on drugstore shelves any time soon.
pet: 1 qt of a 3% hydrogen peroxide
hydrogen sulfide reacts with H2O2 to
solution, 1/4 cup of baking soda, and
form sulfate compounds that do not Questions
1 tsp of liquid soap. His friend tried it
have a bad odor. 1. How did Paul Krebaum’s
out, and the result was one wet and
research into the properties of
2NaOH + 4H2O2 + H2S ⎯→ unhappy—but much less smelly—
H2S result in a benefit to dog
Na2SO4 + 6H2O pet.
Mr. Krebaum says that the hydro- owners?
“The receptors that are in your gen peroxide in the remedy actually 2. What are some possible packag-
nose are sensitive to sulfur in its low oxidizes the compounds, while the ing designs that Paul Krebaum
oxidation state,” says Mr. Krebaum. baking soda reduces the acidity of could have used if he had
“However, they are not sensitive to the mixture and the soap helps to wanted to sell his formula?
sulfur in its high oxidation state.” wash out the greasy skunk spray.
Some time later, a friend of This reaction can be seen in the fol-
Mr. Krebaum’s complained to him lowing equation. The symbol R repre-
that a skunk had sprayed his pet. sents all the other elements in the
636 CHAPTER 19
Balancing Redox SECTION 2
Equations OBJECTIVES
Explain what must be con-
served in redox equations.
Balance redox equations

E quations for simple redox reactions can be balanced by inspection, by using the half-reaction
which you learned to do in Chapter 8. Most redox equations, however, method.
require more systematic methods. The equation-balancing process
requires the use of oxidation numbers. In a balanced equation, both
charge and mass are conserved. Although oxidation and reduction half-
reactions occur together, their reaction equations are balanced sepa-
rately and then combined to give the balanced redox-reaction equation.
Half-Reaction Method
The half-reaction method, or ion-electron method, for balancing redox C ROSS -D ISCIPLINARY
equations consists of seven steps. Oxidation numbers are assigned to all Go to go.hrw.com for a full-length
atoms and polyatomic ions to determine which species are part of the article on redox reactions in photo-
redox process. The oxidation and reduction equations are balanced sep- synthesis.
arately for mass and charge. They are then added together to produce a Keyword: HC6OXRX
complete balanced equation. These seven steps are applied to balance
the reaction of hydrogen sulfide and nitric acid. Sulfuric acid, nitrogen
dioxide, and water are the products of the reaction.
1. Write the formula equation if it is not given in the problem. Then
write the ionic equation.
Formula equation: H2S + HNO3 ⎯→ H2SO4 + NO2 + H2O
Ionic equation: H2S + H+ + NO−3 ⎯→ 2H+ + SO2−
4 + NO2 + H2O
2. Assign oxidation numbers. Delete substances containing only el-

ements that do not change oxidation state.
+1 −2 +1 +5 −2 +1 +6 −2 +4 −2 +1 −2
H2S + H+ + NO 3− ⎯→ 2H+ + SO 2−
4 + NO2 + H2O
The sulfur changes oxidation state from −2 to +6. The nitrogen

changes oxidation state from +5 to +4. The other substances are
deleted.
+1 −2 +5 −2 +6 −2 +4 −2
H2S + NO 3− ⎯→ SO 2−
4 + NO2
The remaining species are used in step 3.

3. Write the half-reaction for oxidation. In this example, the sulfur is
being oxidized.
−2 +6
H2S ⎯→ SO 2−
4
• Balance the atoms. To balance the oxygen in this half-reaction, H2O

must be added to the left side. This gives 10 extra hydrogen atoms on
that side of the equation. Therefore, 10 hydrogen ions are added to
the right side. In basic solution, OH − ions and water may be used to
balance atoms.
−2 +6
+
H2S + 4H2O ⎯→ SO 2−
4 + 10H
• Balance the charge. Electrons are added to the side having the
greater positive net charge. The left side of the equation has no net
charge; the right side has a net charge of 8+. For the charges to bal-
ance, each side must have the same net charge. Therefore, 8 electrons
are added to the product side so that it has no charge and balances
with the reactant side of the equation. Notice that the oxidation of
sulfur from a state of −2 to +6 indicates a loss of 8 electrons.
−2 +6
+ −
H2S + 4H2O ⎯→ SO 2−
4 + 10H + 8e
The oxidation half-reaction is now balanced.
4. Write the half-reaction for reduction. In this example, nitrogen is

being reduced from a +5 state to a +4 state.
+5 +4
NO3− ⎯→ NO2
• Balance the atoms. H2O must be added to the product side of the
reaction to balance the oxygen atoms. Therefore, two hydrogen ions
must be added to the reactant side to balance the hydrogen atoms.
+5 +4
NO3− + 2H+ ⎯→ NO2 + H2O
• Balance the charge. Electrons are added to the side having the
greater positive net charge. The left side of the equation has a net
charge of 1+. Therefore, 1 electron must be added to this side to bal-
ance the charge.
+5 +4
NO3− + 2H+ + e− ⎯→ NO2 + H2O
The reduction half-reaction is now balanced.
5. Conserve charge by adjusting the coefficients in front of the elec-

trons so that the number lost in oxidation equals the number gained
in reduction. Write the ratio of the number of electrons lost to the
number of electrons gained.
e− lost in oxidation 8
=
e− gained in reduction 1
638 CHAPTER 19
This ratio is already in its lowest terms. If it were not, it would need
to be reduced. Multiply the oxidation half-reaction by 1 (it remains KMnO4
unchanged) and the reduction half-reaction by 8. The number of
electrons lost now equals the number of electrons gained.
−2 +6

1 H2S + 4H2O ⎯→ SO 42− + 10H+ + 8e−
+5 +4

8 NO −3 + 2H+ + e− ⎯→ NO2 + H2O
6. Combine the half-reactions, and cancel out anything common to
both sides of the equation.
−2 +6
H2S + 4H2O ⎯→ SO42− + 10H+ + 8e−
+5 +4 FeSO4
8 NO −3 + 16H+ + 8e− ⎯→ 8 NO2 + 8H2O in H2SO4
+5 6 −2
8NO −3 + 16H+ + 8e− + H2S + 4H2O ⎯→
+4 4 +6
FIGURE 4 As a KMnO4 solution
8NO2 + 8H2O + SO 42− + 10H+ + 8e−
is titrated into an acidic solution of
FeSO4, deep purple MnO −4 ions are
Each side of the above equation has 10H+, 8e−, and 4H2O. These can- reduced to colorless Mn2+ ions.
cel each other out and do not appear in the balanced equation. When all Fe2+ ions are oxidized,
+5 −2 +4 +6 MnO −4 ions are no longer reduced
8NO −3 + H2S + 6H+ ⎯→ 8NO2 + 4H2O + SO 42− to colorless Mn2+ ions. Thus, the first
faint appearance of the MnO −4 color
7. Combine ions to form the compounds shown in the original formu- indicates the end point of the
titration.
la equation. Check to ensure that all other ions balance. The NO−3
ion appeared as nitric acid in the original equation. There are only
6 hydrogen ions to pair with the 8 nitrate ions. Therefore, 2 hydrogen
ions must be added to complete this formula. If 2 hydrogen ions are
added to the left side of the equation, 2 hydrogen ions must also be
added to the right side of the equation.
8HNO3 + H2S ⎯→ 8NO2 + 4H2O + SO 2− +
4 + 2H
The sulfate ion appeared as sulfuric acid in the original equation. The
hydrogen ions added to the right side are used to complete the form-
ula for sulfuric acid.
8HNO3 + H2S ⎯→ 8NO2 + 4H2O + H2SO4
A final check must be made to ensure that all elements are correctly
balanced.
Write a balanced equation for the reaction shown in Figure 4. A deep purple solution of potassium per-
manganate is titrated with a colorless solution of iron(II) sulfate and sulfuric acid. The products are
iron(III) sulfate, manganese(II) sulfate, potassium sulfate, and water—all of which are colorless.

SOLUTION 1. Write the formula equation if it is not given in the problem. Then write the ionic equation.
KMnO4 + FeSO4 + H2SO4 ⎯→ Fe2(SO4)3 + MnSO4 + K2SO4 + H2O

K+ + MnO−4 + Fe2+ + SO2− +
4 + 2H + SO4 ⎯→
2−
2Fe3+ + 3SO2− +
4 + Mn + SO4 + 2K + SO4 + H2O
2+ 2− 2−
2. Assign oxidation numbers to each element and ion. Delete substances containing an ele-
ment that does not change oxidation state.
+1 +7 −2 +2 +6 −2 +1 +6 −2
K+ + MnO−4 + Fe2+ + SO2− +
4 + 2H + SO4 ⎯→
2−
+3 +6 −2 +2 +6 −2 +1 +6 −2 +1 −2
2Fe3+ + 3SO2− +
4 + Mn + SO4 + 2K + SO4 + H2O
2+ 2− 2−
Only ions or molecules whose oxidation numbers change are retained.

+7 −2 +2 +3 +2
MnO−4 + Fe2+ ⎯→ Fe3+ + Mn2+
3. Write the half-reaction for oxidation. The iron shows the increase in oxidation number.
Therefore, it is oxidized.
+2 +3
Fe2+ ⎯→ Fe3+
• Balance the mass. The mass is already balanced.
• Balance the charge.

+2 +3
Fe2+ ⎯→ Fe3+ + e−
4. Write the half-reaction for reduction. Manganese shows a change in oxidation number
from +7 to +2. It is reduced.
+7 +2
MnO−4 ⎯→ Mn2+
• Balance the mass. Water and hydrogen ions must be added to balance the oxygen atoms
in the permanganate ion.
+7 +2
MnO−4 + 8H+ ⎯→ Mn2+ + 4H2O
• Balance the charge.

+7 +2
MnO−4 + 8H+ + 5e− ⎯→ Mn2+ + 4H2O
5. Adjust the coefficients to conserve charge.

e− lost in oxidation 1
=
e− gained in reduction 5
5(Fe2+ ⎯→ Fe3+ + e−)

1(MnO−4 + 8H+ + 5e− ⎯→ Mn2+ + 4H2O)
640 CHAPTER 19
6. Combine the half-reactions and cancel.
5Fe2+ ⎯→ 5Fe3+ + 5e−

MnO−4 + 8H+ + 5e− ⎯→ Mn2+ + 4H2O
MnO−4 + 5Fe2+ + 8H+ + 5e− ⎯→ Mn2+ + 5Fe3+ + 4H2O + 5e−
7. Combine ions to form compounds from the original equation. The iron(III) product
appears in the original equation as Fe2(SO4)3. Every iron(III) sulfate molecule requires
two iron ions. Therefore, the entire equation must be multiplied by 2 to provide an even
number of iron ions.
2(5Fe2+ + MnO−4 + 8H+ ⎯→ 5Fe3+ + Mn2+ + 4H2O)

10Fe2+ + 2MnO−4 + 16H+ ⎯→ 10Fe3+ + 2Mn2+ + 8H2O
The iron(II), iron(III), manganese(II), and 2 hydrogen ions in the original equation are
paired with sulfate ions. Iron(II) sulfate requires 10 sulfate ions, and sulfuric acid
requires 8 sulfate ions. To balance the equation, 18 sulfate ions must be added to each
side. On the product side, 15 of these ions form iron(III) sulfate, and 2 of them form man-
ganese(II) sulfate. That leaves 1 sulfate ion unaccounted for. The permanganate ion
requires the addition of 2 potassium ions to each side. These 2 potassium ions form
potassium sulfate on the product side of the reaction.
10FeSO4 + 2KMnO4 + 8H2SO4 ⎯→ 5Fe2(SO4)3 + 2MnSO4 + K2SO4 + 8H2O
Final inspection shows that atoms and charges are balanced.
1. Copper reacts with hot, concentrated sulfuric acid to form cop-

per(II) sulfate, sulfur dioxide, and water. Write and balance the
equation for this reaction.
2. Write and balance the equation for the reaction between nitric Go to go.hrw.com for
acid and potassium iodide. The products are potassium nitrate, more practice problems
iodine, nitrogen monoxide, and water. that ask you to balance
redox equations.
Keyword: HC6OXRX
SECTION REVIEW Critical Thinking

1. What two quantities are conserved in redox 4. RELATING IDEAS When heated, elemental phos-
equations? phorus, P4, produces phosphine, PH3, and phos-
2. Why do we add H+ and H2O to some half- phoric acid, H3PO4. How many grams of phosphine
reactions and OH− and H2O to others? are produced if 56 g P4 have reacted?
3. Balance the following redox reaction:
Na2SnO2 + Bi(OH)3 ⎯→ Bi + Na2SnO3 + H2O

SECTION 3
Oxidizing and
OBJECTIVES Reducing Agents
Relate chemical activity to
oxidizing and reducing
strength.
Explain the concept of A reducing agent is a substance that has the potential to cause another
disproportionation. substance to be reduced. Reducing agents lose electrons; they attain a
more positive oxidation state during an oxidation-reduction reaction.
Therefore, the reducing agent is the oxidized substance.
An oxidizing agent is a substance that has the potential to cause an-
other substance to be oxidized. Oxidizing agents gain electrons and
attain a more negative oxidation state during an oxidation-reduction
reaction. The oxidizing agent is the reduced substance. Table 2 helps
clarify the terms describing the oxidation-reduction process.
Strengths of Oxidizing
and Reducing Agents
Different substances can be compared and rated by their relative
potential as reducing and oxidizing agents. For example, the order of the
elements in the activity series (see Table 3 on page 286) is related to each
element’s tendency to lose electrons. Elements in this series lose elec-
trons to the positively charged ions of any element below them in the
series. The more active an element is, the greater its tendency to lose
electrons and the better a reducing agent it is. The greater the distance
is between two elements in the list, the more likely it is that a redox
reaction will take place between them.
These elements and some other familiar substances are arranged in
Table 3 according to their activity as oxidizing and reducing agents. The
fluorine atom is the most highly electronegative atom. It is also the most
TABLE 2 Oxidation-Reduction Terminology

Change in Change in
Term oxidation number electron population
Oxidation in a positive direction loss of electrons
Reduction in a negative direction gain of electrons
Oxidizing agent in a negative direction gains electrons
Reducing agent in a positive direction loses electrons
642 CHAPTER 19
active oxidizing agent. Because of its strong attraction for its own elec- TABLE 3 Relative Strength
trons, the fluoride ion is the weakest reducing agent. The negative ion of of Oxidizing and Reducing
a strong oxidizing agent is a weak reducing agent. Agents
The positive ion of a strong reducing agent is a weak oxidizing agent.
Reducing Oxidizing
As shown in Table 3, Li atoms are strong reducing agents because Li is
agents agents
a very active metal. When Li atoms oxidize, they produce Li+ ions, which
Li+
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→
are unlikely to reacquire electrons, so Li+ ions are weak oxidizing Li
agents. K K+
The left column of each pair also shows the relative abilities of met- Ca Ca2+
als listed in the table to displace other metals from their compounds.
Na Na+
Zinc, for example, appears above copper. Thus, zinc is the more active
reducing agent, and it displaces copper ions from solutions of copper Mg Mg2+
compounds, as illustrated in Figure 5. The copper(II) ion, on the other Al Al3+
hand, is a more active oxidizing agent than the zinc ion. Zn Zn2+
Nonmetals and some important ions also are included in the series in Cr Cr3+
Table 3. Any reducing agent is oxidized by the oxidizing agents below
Fe Fe2+
it. Observe that F2 displaces Cl −, Br−, and I − ions from their solutions.
Cl2 displaces Br− and I − ions, and Br2 displaces I − ions. The equation for Ni Ni2+
the displacement of Br− by Cl2 is as follows. Sn Sn2+
Pb Pb2+
Cl2 + 2Br−(aq) ⎯→ 2Cl −(aq) + Br2
Increasing strength
Increasing strength
H2 H3O+
−1 0
2 Br− ⎯→ Br2 + 2e− (oxidation) H2S S
0 −1 Cu Cu2+
Cl2 + 2e− ⎯→ 2 Cl − (reduction) I− I2
MnO 2−4 MnO −4
In every redox reaction, there is one reducing agent and one oxi- 2+
dizing agent. In the preceding example, Br− is the reducing agent and Fe Fe3+
Cl2 is the oxidizing agent. Hg Hg2+
2
Ag Ag+
NO −2 NO −3
Br− Br2
Mn2+ MnO2
SO2 H2SO4 (conc.)
Cr3+ Cr2O 2−
7
Cl − Cl2
Mn2+ MnO −4
F− F2
FIGURE 5 Zinc displaces copper ions from a copper(II) sulfate solution.

Metallic copper precipitates.

Wear safety goggles and an apron.
Materials
Redox Reactions • aluminum foil
• beaker, 250 mL
Procedure • 1 M copper(II) chloride solu-
Record all of your results in a tion, CuCl2
data table. • 3% hydrogen peroxide
1. Put 10 mL of hydrogen perox- Discussion • manganese dioxide
ide in a test tube, and add a • metric ruler
small amount of manganese
1. Write balanced equations
• scissors
showing what happened in
dioxide (equal to the size of • test-tube clamp
each of the reactions.
about half a pea). What is the • test tube, 16 × 150 mm
result? 2. Write a conclusion for the two • wooden splint
experiments.
2. Insert a glowing wooden splint
into the test tube (see dia-
Wooden
gram). What is the result? If splint
oxygen is produced, a glowing
wooden splint inserted into the
test tube will glow brighter.
3. Fill the 250 mL beaker halfway
with the copper(II) chloride
solution.
Clamp
4. Cut foil into 2 cm × 12 cm
strips.
5. Add the aluminum strips to the
copper(II) chloride solution. H2O2
Use a glass rod to stir the mix-
ture, and observe for 12 to
15 minutes. What is the result?
Disproportionation
Some substances can be both reduced and oxidized easily. For example,
peroxide ions, O 2−
2 , have a relatively unstable covalent bond between
the two oxygen atoms. The electron-dot formula is written as follows.
2−
O O
Each oxygen atom has an oxidation number of −1. The peroxide ion
structure represents an intermediate oxidation state between O2 and
O2−. Therefore, the peroxide ion is highly reactive.
Hydrogen peroxide, H2O2, is a covalent compound. It decomposes
into water and molecular oxygen, as shown in the equation below.
−1 −2 0
2H2O2 ⎯→ 2H2O + O2
644 CHAPTER 19
FIGURE 6 A bombardier beetle
can repel large predators such as
frogs with a chemical defense mech-
anism that uses the disproportiona-
tion of hydrogen peroxide.
Notice that in this reaction, hydrogen peroxide is both oxidized and

reduced. Oxygen atoms that become part of gaseous oxygen molecules
are oxidized. The oxidation number of these oxygen atoms increases
from −1 to 0. Oxygen atoms that become part of water are reduced. The
oxidation number of these oxygen atoms decreases from −1 to −2. A
process in which a substance acts as both an oxidizing agent and a reduc-
ing agent is called disproportionation. A substance that undergoes dis-
proportionation is both self-oxidizing and self-reducing.
The bombardier beetle defends itself by spraying its enemies with an
unpleasant hot chemical mixture, as shown in Figure 6. The catalyzed
disproportionation of hydrogen peroxide produces hot oxygen gas. This
gas gives the insect an ability to eject irritating chemicals from its
abdomen with explosive force.
SECTION REVIEW 2. The photo on the left depicts two redox reactions.
1. Describe the chemical activity of the alkali metals Both nails are in a sulfuric acid solution. Answer
and of the halogens on the basis of oxidizing and the following questions:
reducing strength. a. When zinc is wrapped around an iron nail,
is the iron or zinc oxidized?
b. When copper is wrapped around an iron
nail, is the iron or copper oxidized?
3. Would Cl2 be reduced by I−? Explain.
4. Which is the stronger oxidizing agent in each of
the following pairs: Cu2+ or Al3+, I2 or S, F2 or Li+?
5. What is meant by disproportionation?
Critical Thinking
6. ORGANIZING IDEAS In general, where in the
periodic table are the elements found that in
elemental form are the strongest oxidizing
agents? Explain.

CHAPTER HIGHLIGHTS
Oxidation and Reduction
Vocabulary • Oxidation numbers are assigned by the set of rules listed in
oxidation Table 1. Oxidation numbers are based on the distribution of
oxidized electrons in a molecule.
reduction • Oxidation-reduction reactions consist of two half-reactions
reduced that must occur simultaneously.
oxidation-reduction reaction • Oxidation-reduction reactions are identified by examining the
redox reaction changes in the oxidation numbers of atoms in the reactants
half-reaction and products.
• Oxidation involves the loss of electrons, and reduction involves
the gain of electrons.
• A species whose oxidation number increases is oxidized. A
species whose oxidation number decreases is reduced.
Balancing Redox Equations

• Charge and mass are conserved in a balanced redox equation.
• In the half-reaction method for balancing equations, the atoms
and charge of oxidation and reduction equations are balanced
separately. Then, they are combined to give a complete balanced
equation.
• In a half-reaction, the charge on the reactant side must equal
the charge on the product side, but these charges do not need
to be zero.
• For the half-reaction method, the atoms in each half-reaction
are balanced by adding H+ ions and H2O molecules in acidic
solutions. If the solution is basic, OH− ions and H2O molecules
are added to balance the atoms in each half-reaction.
• The number of electrons lost in the oxidation half-reaction
must equal the number of electrons gained in the reduction
half-reaction. The two half-reactions must be multiplied by
appropriate factors to ensure that the same number of elec-
trons are transferred.
Oxidizing and Reducing Agents

Vocabulary • The substance that is reduced in redox reactions is the oxidiz-
reducing agent ing agent because it acquires electrons from the substance that
oxidizing agent is oxidized.
disproportionation • The substance that is oxidized in a redox reaction is the reducing
agent because it supplies the electrons to the substance that is
reduced.
• Strong reducing agents are substances that easily give up elec-
trons.
• Disproportionation is a process in which a substance is both an
oxidizing agent and a reducing agent.
646 CHAPTER 19
CHAPTER REVIEW
For more practice, go to the Problem Bank in Appendix D.
Oxidation and Reduction 7. Determine the oxidation number of each atom

indicated in the following:
SECTION 1 REVIEW a. H2 f. HNO3
1. a. Distinguish between the processes of oxida- b. H2O g. H2SO4
tion and reduction. c. Al h. Ca(OH)2
b. Write an equation to illustrate each process. d. MgO i. Fe(NO3)2
2. Which of the following are redox reactions? e. Al2S3 j. O2
a. 2Na + Cl2 ⎯→ 2NaCl
b. C + O2 ⎯→ CO2
c. 2H2O ⎯→ 2H2 + O2
Balancing Redox Equations
d. NaCl + AgNO3 ⎯→ AgCl + NaNO3 SECTION 2 REVIEW
e. NH3 + HCl ⎯→ NH +4 + Cl − 8. Label the following half-reactions as either
f. 2KClO3 ⎯→ 2KCl + 3O2 reduction or oxidation half-reactions.
g. H2 + Cl2 ⎯→ 2HCl a. H2S ⎯→ S + 2e− + 2H+
h. H2SO4 + 2KOH ⎯→ K2SO4 + 2H2O b. SO2 + 4e− + 2H2O ⎯→ S + 4OH−
i. Zn + CuSO4 ⎯→ ZnSO4 + Cu c. ClO−3 + 6H+ + 6e− ⎯→ Cl− + 3H2O
3. For each oxidation-reduction reaction in the −
d. Mn(CN)4− 6 ⎯→ Mn(CN)6 + e
3−
previous question, identify what is oxidized and 9. What are the oxidation states of the elements
what is reduced. that changed oxidation states in the half-
reactions in the above question?
PRACTICE PROBLEMS 10. Balance the equation for the following reaction
4. Each of the following atom/ion pairs undergoes in a basic solution. Give balanced equations for
the oxidation number change indicated below. both half-reactions and the balanced equation
For each pair, determine whether oxidation or for the overall reaction.
reduction has occurred, and then write the elec- KMnO4 + NaIO3 ⎯→ MnO2 + NaIO4
tronic equation indicating the corresponding
number of electrons lost or gained. PRACTICE PROBLEMS
a. K ⎯→ K+ e. H2 ⎯→ H+ 11. For each requested step, use the half-reaction
b. S ⎯→ S 2− f. O2 ⎯→ O2− method to balance the oxidation-reduction
c. Mg ⎯→ Mg 2+ g. Fe3+ ⎯→ Fe2+ equation below. (Hint: See Sample Problem A.)
d. F − ⎯→ F2 h. Mn2+ ⎯→ MnO4– K + H2O ⎯→ KOH + H2
5. Identify the following reactions as redox or a. Write the ionic equation, and assign oxida-
nonredox: tion numbers to all atoms to determine what
a. 2NH4Cl(aq) + Ca(OH)2(aq) ⎯→ is oxidized and what is reduced.
2NH3(aq) + 2H2O(l) + CaCl2(aq) b. Write the equation for the reduction, and
b. 2HNO3(aq) + 3H2S(g) ⎯→ balance it for both atoms and charge.
2NO(g) + 4H2O(l) + 3S(s) c. Write the equation for the oxidation, and
c. [Be(H2O)4]2+(aq) + H2O(l) ⎯→ balance it for both atoms and charge.
H3O+(aq) + [Be(H2O)3OH]+(aq) d. Multiply the coefficients of the oxidation and
6. Arrange the following in order of increasing reduction equations so that the number of
oxidation number of the xenon atom: CsXeF8, electrons lost equals the number of electrons
Xe, XeF2, XeOF2, XeO3, and XeF. gained. Add the two equations.
e. Add species as necessary to balance the
overall formula equation.

CHAPTER REVIEW
12. Use the method in the previous problem to bal- 18. Arrange the following in order of decreasing
ance each of the reactions below. oxidation number of the nitrogen atom: N2,
a. HI + HNO2 ⎯→ NO + I2 + H2O NH3, N2O4, N2O, N2H4, and NO−3 .
b. FeCl3 + H2S ⎯→ FeCl2 + HCl + S 19. Balance the following redox equations:
13. Balance the equation for the reaction in a. SbCl5 + KI ⎯→ KCl + I2 + SbCl3
which hot, concentrated sulfuric acid reacts with b. Ca(OH)2 + NaOH + ClO2 + C ⎯→
zinc to form zinc sulfate, hydrogen sulfide, NaClO2 + CaCO3 + H2O
and water. 20. Balance the following equations in basic
solution:
a. PbO2 + KCl ⎯→ KClO + KPb(OH)3
Oxidizing and Reducing b. KMnO4 + KIO3 ⎯→ MnO2 + KIO4
c. K2MnO4 ⎯→ MnO2 + KMnO4
Agents 21. Balance the following equations in acidic
SECTION 3 REVIEW solution:
a. MnO−4 + Cl− ⎯→ Mn2+ + HClO
14. a. Identify the most active reducing agent
b. NO−3 + I2 ⎯→ IO−3 + NO2
among all common elements.
c. NO−2 ⎯→ NO + NO−3
b. Why are all of the elements in its group in the
periodic table very active reducing agents?
c. Identify the most active oxidizing agent
among the common elements.
CRITICAL THINKING
15. Use Table 3 to identify the strongest and weak- 22. Interpreting Graphics Given the activity table
est reducing agents among the substances listed below, determine whether a reaction will occur or
within each of the following groupings: not. If the reaction will occur, give the products.
a. Ca, Ag, Sn, Cl−
b. Fe, Hg, Al, Br− Reducing
Agents
c. F −, Pb, Mn2+, Na
L L+
16. Use Table 3 to respond to each of the following: M M+
a. Would Al be oxidized by Ni2+? P P+
b. Would Cu be oxidized by Ag+? T T+
c. Would Pb be oxidized by Na+?
Oxidizing
d. Would F2 be reduced by Cl−? Agents
e. Would Br2 be reduced by Cl−?
a. L and M+
b. P and M+
MIXED REVIEW c. P and T +
23. Drawing Conclusions A substance has an ele-
17. Identify the following reactions as redox or ment in one of its highest possible oxidation
nonredox: states. Is this substance more likely to be an oxi-
a. Mg(s) + ZnCl2(aq) ⎯→ Zn(s) + MgCl2(aq) dizing agent or a reducing agent? Explain your
b. 2H2(g) + OF2(g) ⎯→ H2O(g) + 2HF(g) reasoning.
c. 2KI(aq) + Pb(NO3)2(aq) ⎯→
PbI2(s) + 2KNO3(aq)
d. CaO(s) + H2O(l) ⎯→ Ca(OH)2(aq)
e. 3CuCl2(aq) + 2(NH4)3PO4(aq) ⎯→
6NH4Cl(aq) + Cu3(PO4)2(s)
f. CH4(g) + 2O2(g) ⎯→ CO2(g) + 2H2O(g)
648 CHAPTER 19
CHAPTER REVIEW
24. Drawing Conclusions Use Table 3 to decide if RESEARCH & WRITING

a redox reaction would occur between the two
species, and if so, write the balanced equation. 28. Oxidizing agents are used in the cleaning indus-
Explain your reasoning. try. Research three different oxidizing agents
a. Cl2 and Br2 used in this area, and write a report on the advan-
b. Sn2+ and Zn tages and disadvantages of these compounds.
25. Drawing Conclusions An element that dispro- 29. Oxidizing and reducing agents play important
portionates must have at least how many differ- roles in biological systems. Research the role of
ent oxidation states? Explain your reasoning. one of these agents in a biological process.
Write a report describing the process and the
role of oxidation and reduction.
USING THE HANDBOOK
26. Several reactions of aluminum are shown in the ALTERNATIVE ASSESSMENT
common reactions section for Group 13 of the
Elements Handbook. Use these reactions to 30. Boilers are used to convert water to steam in
answer the following: electric power plants. Dissolved oxygen in the
a. Which of the five reactions shown are water promotes corrosion of the steel used in
oxidation-reduction reactions? How do boiler parts. Explain how dissolved oxygen is
you know? removed from the water in boilers.
b. For each redox reaction you listed in item a, 31. Performance For one day, record situations
identify what is oxidized and what is reduced. that show evidence of oxidation-reduction reac-
c. Write half-reactions for each equation you tions. Identify the reactants and the products,
listed in item a. and determine whether there is proof that a
27. Aluminum is described in Group 13 of the chemical reaction has taken place.
Elements Handbook as a self-protecting metal.
This property of aluminum results from a redox
reaction.
a. Write the redox equation for the oxidation of
aluminum.
b. Write the half-reactions for this reaction, and
show the number of electrons transferred.
c. What problems are associated with the
buildup of aluminum oxide on electrical
wiring made of aluminum?

Math Tutor BALANCING REDOX EQUATIONS
A redox equation must conserve both mass and charge. So, to balance a redox equation,
you must balance both atoms and charge (electrons). The problem-solving tips and sam-
ple below show how to balance an equation for a redox reaction in basic solution.
Problem-Solving S
To balance redox equations for reactions in basic solution:
• Add OH− and H2O to balance oxygen and hydrogen in the redox half-reactions.
• Add OH− ions to the side of the equation that needs oxygen atoms. Make sure
you add enough OH− ions so that the number of oxygen atoms added is twice the
number needed.
• Then, add enough H2O molecules to the other side of the equation to balance the
hydrogen atoms.
SAMPLE
The following unbalanced equation represents a redox reaction that takes place in a basic
solution containing KOH. Balance the redox equation.
Br2(l) + KOH(aq) ⎯→ KBr(aq) + KBrO3(aq)
Write the full ionic equation, assign oxidation numbers, and eliminate species whose oxi-
dation numbers do not change. The result is the following equation:
0 −1 +5
Br2 ⎯→ Br− + BrO−3
Divide this equation into half-reactions. Note that Br2 is the reactant in both half-reactions.
Reduction: Br2 ⎯→ Br− Oxidation: Br2 ⎯→ BrO−3
−
Add H2O and OH to balance atoms in basic solution. Then, add electrons to balance charge.
Reduction: Br2 + 2e− ⎯→ 2Br− (no need to add H2O or OH− )
Oxidation: 12OH− + Br2 ⎯→ 2BrO−3 + 6H2O + 10e−
To balance transferred electrons, you must multiply the reduction half-reaction by 5 so that
both reactions have 10e−.
5 × (Br2 + 2e− ⎯→ 2Br−) = 5Br2 + 10e− ⎯→ 10Br−
Combining the two half-reactions gives
5Br2 + 12OH− + Br2 + 10e− ⎯→ 10Br− + 2BrO−3 + 6H2O + 10e−
Canceling common species gives
6Br2 + 12OH− ⎯→ 10Br− + 2BrO−3 + 6H2O
Returning the potassium ions to the equation gives
6Br2 + 12KOH ⎯→ 10KBr + 2KBrO3 + 6H2O, or 3Br2 + 6KOH ⎯→
5KBr + KBrO3 + 3H2O
PRACTICE PROBLEMS
1. Balance the following equation for a redox 2. Balance the following equation for a redox
reaction that takes place in basic solution: reaction that takes place in basic solution:
MnO2(s) + NaClO3(aq) + NaOH(aq) ⎯→ N2O(g) + KClO(aq) + KOH(aq) ⎯→
NaMnO4(aq) + NaCl(aq) + H2O(l) KCl(aq) + KNO2(aq) + H2O(l)
650 CHAPTER 19
Answer the following items on a separate piece of paper. 7. Arrange the following in order of increasing
MULTIPLE CHOICE
oxidation number of the sulfur atom: S2O2−3 ,
S4O2− , HSO −, and H S.
6 4 2
1. In the following reaction, which species is 2−, HSO−
A. H2S, S2O2−3 , S O
4 6 4
reduced?
B. S2O2− 2− −
2K + Br2 ⎯→ 2K+ + 2Br− 3 , H2S, S4O6 , HSO4
2− −
C. H2S, S2O3 , HSO4 , S4O6 2−
A. K
B. Br2 D. HSO−4 , S2O2− 2−
3 , S4O6 , H2S
C. All of the above 8. Which answer contains the correct information
D. None of the above about the following reaction:
2. The oxidation number of the sulfur atom in the 2Pb(NO3)2 ⎯→ 2PbO + 4NO2 + O2
SO2−
4 ion is A. This reaction is a decomposition reaction and
A. +2. not a redox reaction.
B. −2. B. This reaction is a redox reaction in which the
C. +6. lead is reduced and the oxygen is oxidized.
D. +4. C. This reaction is a disproportionation reaction.
3. A half-reaction D. This reaction is a redox reaction in which the
A. involves a change in the oxidation state of an nitrogen is reduced and the oxygen is oxidized.
element. SHORT ANSWER
B. always contains H2O molecules. 9. Determine the oxidation numbers for Cu in the
C. always contains H+ ions. superconductor YBa2Cu3O7. Yttrium (Y) has an
D. All of the above oxidation number of +3. (Cu does not have oxi-
4. In the following reaction, which is the oxidizing dation numbers greater than +3.) Give only
agent? integer oxidation numbers.
AgNO2 + Cl2 + 2KOH ⎯→ 10. What is an oxidizing agent?
AgNO3 + 2KCl + H2O
EXTENDED RESPONSE
A. AgNO2
B. Cl2 11. B, F, K, and L are four unknown reducing
C. KOH agents that oxidize to singly charged cations.
D. KCl Using the following information, construct a
table showing the relative strengths of the oxi-
5. What are the oxidation states (in increasing dizing and reducing agents. Data: F reduces K+,
order) of the element that undergoes dispropor- B+, and L+. B+ oxidizes K and F, but not L.
tionation in the following reaction:
Cl2 + H2O ⎯→ HCl + HOCl 12. Balance the equation for the following reaction
A. −1, 0, +2
in basic solution:
B. −1, 0, +1 ClO2 ⎯→ KClO3 + KClO2
C. −2, −1, 0 Give the balanced equation for each half-
D. None of the above reaction and for the overall reaction. Give the
6. Which reaction is a redox reaction? oxidizing agent and the reducing agent.
A. Al2O3 + 6HCl ⎯→ 2AlCl3 + 3H2O
B. 2HCO−3 ⎯→ CO2 + CO2− 3 + H2O
C. SiBr4 + 3H2O ⎯→ H2SiO3 + 4HBr
D. H2O + PbO2 + NaOH + KCl ⎯→ If you are short on time, quickly
KClO + NaPb(OH)3 scan the unanswered questions to see which might
be easiest to answer.

SEE PRE-LAB MICRO
CHAPTER LAB VOLUMETRIC ANALYSIS L A B
Reduction of Manganese
in Permanganate Ion
• Demonstrate proficiency in performing In Chapter 15, you studied acid-base titrations in
redox titrations and recognizing end points which an unknown amount of acid is titrated with a
of a redox reaction. carefully measured amount of base. In this procedure,
• Write a balanced oxidation-reduction a similar approach called a redox titration is used. In a
equation for a redox reaction. redox titration, the reducing agent, Fe2+, is oxidized to
Fe3+ by the oxidizing agent, MnO−4 . When this process
• Determine the concentration of a solution occurs, the Mn in MnO−4 changes from a +7 to a +2
by using stoichiometry and volume data oxidation state and has a noticeably different color.
from a titration.
You can use this color change to signify a redox reac-
tion “end point.” When the reaction is complete, any
MATERIALS
excess MnO−4 added to the reaction mixture will give
• 0.0200 M KMnO4 the solution a pink or purple color. The volume data
• 1.0 M H2SO4 from the titration, the known molarity of the KMnO4
solution, and the mole ratio from the balanced redox
• 100 mL graduated cylinder equation will give you the information you need to
• 125 mL Erlenmeyer flasks, 4 calculate the molarity of the FeSO4 solution.
• 250 mL beakers, 2
SAFETY
• 400 mL beaker
• burets, 2
• distilled water
For review of safety, please see Safety in the
• double buret clamp Chemistry Laboratory in the front of your book.
• FeSO4 solution
PREPARATION
• ring stand
1. In your lab notebook, prepare a data table like
• wash bottle
the one shown on the next page.
2. Clean two 50 mL burets with a buret brush and
distilled water. Rinse each buret at least three
times with distilled water to remove contaminants.
3. Label one 250 mL beaker “0.0200 M KMnO4”
and the other “FeSO4.” Label three of the flasks
“1,” “2,” and “3.” Label the 400 mL beaker
“Waste.” Label one buret “KMnO4” and the other
“FeSO4.”
652 CHAPTER 19
DATA TABLE
Trial Initial KMnO4 Final KMnO4 Initial FeSO4 Final FeSO4
volume (mL) volume (mL) volume (mL) volume (mL)
1
2
3
4. Measure approximately 75 mL of 0.0200 M 2. Slowly add KMnO4 from the buret to the FeSO4
KMnO4, and pour it into the appropriately in the flask while swirling the flask. When the
labeled beaker. Obtain approximately 75 mL color of the solution matches the color standard
of FeSO4 solution, and pour it into the appro- you prepared in Preparation step 8, record in
priately labeled beaker. your data table the final readings of the burets.
5. Rinse one buret three times with a few milliliters 3. Empty the titration flask into the waste beaker.
of 0.0200 M KMnO4 from the appropriately Repeat the titration procedure in steps 1 and 2
labeled beaker. Collect these rinses in the waste with the flasks labeled “2” and “3.”
beaker. Rinse the other buret three times with
small amounts of FeSO4 solution from the CLEANUP AND DISPOSAL
appropriately labeled beaker. Collect these 4. Dispose of the contents of the waste
rinses in the waste beaker. beaker in the container designated by
6. Set up the burets as instructed by your teacher. your teacher. Also, pour the color-
Fill one buret with approximately 50 mL of standard flask into this container. Wash your
0.0200 M KMnO4 from the beaker, and fill the hands thoroughly after cleaning up the area
other buret with approximately 50 mL of the and equipment.
FeSO4 solution from the other beaker.
ANALYSIS AND INTERPRETATION
7. With the waste beaker underneath its tip, open
1. Organizing Ideas: Write the balanced equation
the KMnO4 buret long enough to be sure the
for the redox reaction of FeSO4 and KMnO4.
buret tip is filled. Repeat the process for the
FeSO4 buret. 2. Evaluating Data: Calculate the number of moles
of MnO4− reduced in each trial.
8. Add 50 mL of distilled water to one of the
125 mL Erlenmeyer flasks, and add one drop 3. Analyzing Information: Calculate the number
of 0.0200 M KMnO4 to the flask. Set this mix- of moles of Fe2+ oxidized in each trial.
ture aside to use as a color standard. It can be
4. Applying Conclusions: Calculate the average
compared with the titration mixture to deter-
concentration (molarity) of the iron(II)
mine the end point.
sulfate solution.
PROCEDURE
1. Record in your data table the initial buret read- EXTENSIONS
ings for both solutions. Add 10 mL of the 1. Designing Experiments: What possible sources
hydrated iron(II) sulfate solution, FeSO4•7H2O, of error can you identify with this procedure?
to the flask labeled “1.” Add 5 mL of If you can think of ways to eliminate them, ask
1 M H2SO4 to the FeSO4 solution in this flask. your teacher to approve your plan, and run the
The acid will help keep the Fe2+ ions in the procedure again.
reduced state, which will allow you time to
titrate.

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CHAPTER 17

The Thermite Reaction

Relate activation energy

2HI(g) ⎯→ H2(g) + I2(g)

REACTION KINETICS 561

The second possible mechanism has a three-step pathway.

(a) Effective collision, (b) Collision (c) Collision that has

FIGURE 3 Three possible colli-

According to the collision theory, the two AB molecules must collide in

REACTION KINETICS 563

Products molecules, is endothermic because the water mole-

In its brief existence, the activated complex

REACTION KINETICS 565

ΔEforward = energy of products − energy of reactants

ΔEreverse = energy of reactants − energy of products

Ea = energy of activated complex − energy of reactants

Ea′ = energy of activated complex − energy of products

1. a. Use the method shown in the sample problem to redraw and

2. a. Draw and label an energy diagram similar to the one shown in

SECTION REVIEW 6. What is the difference between an activated com-

REACTION KINETICS 567

Define catalyst, and discuss

Zn(s) + 2HCl(aq) ⎯→ ZnCl2(aq) + H2(g)

REACTION KINETICS 569

FIGURE 7 The number of mole-

2H2O2(l) ⎯→ O2(g) + 2H2O(l)

Rate Laws for Reactions

2H2(g) + 2NO(g) ⎯→ N2(g) + 2H2O(g)

Four moles of reactant gases produce three moles of product gases;

REACTION KINETICS 571

The ∝ is a symbol that is read “is proportional to.”

Using the Rate Law

The reaction rate is represented by R, k is the specific rate constant,

3NO(g) ⎯→ N2O(g) + NO2(g) R = k[NO]2

NO2(g) + CO(g) ⎯→ NO(g) + CO2(g) R = k[NO2]2

2NO2(g) ⎯→ 2NO(g) + O2(g) R = k[NO2]2

2H2O2(aq) ⎯→ 2H2O(l) + O2(g) R = k[H2O2]

Specific Rate Constant

REACTION KINETICS 573

Experiment [HI] (M) Rate (M/s)

[HI] 0.030 M R 4.4 × 10−3 M/s

PRACTICE Answers in Appendix E

1. For the reaction 3A ⎯→ C, the initial concentration of A was 0.2

Experiment [A] (M) [B] (M) Rate (M/s)

REACTION KINETICS 575

PRACTICE Answers in Appendix E

1. The rate of a hypothetical reaction involving L and M is found to

REACTION KINETICS 577

SECTION REVIEW 4. What is meant by a rate law for a chemical

REACTION KINETICS 579

The Reaction Process PRACTICE PROBLEMS

step is NO2 ⎯→ NO + O. Predict a possible

REACTION KINETICS 581

Reaction Rate MIXED REVIEW

a. Determine the rate law for the reaction.

CRITICAL THINKING ALTERNATIVE ASSESSMENT

RESEARCH & WRITING

REACTION KINETICS 583