4

The Major Classes of

Chemical Reactions

Figure: The universality of chemical

Chapter Outline change. Sparks fly as iron reacts with
4.1 The Role of Water as a Solvent Oxidation Numbers oxygen, one example from one class of
Solubility of Ionic Compounds Balancing Redox Equations the myriad reactions that chemists
Polar Nature of Water Redox Titrations examine. Within each of the surround-
4.2 Precipitation Reactions and Acid- 4.4 Counting Reactants and Products ing red blood cells, an example of a
Base Reactions in Precipitation, Acid-Base, and Redox
very different class of reactions, still
Driving Aqueous Ionic Reactions Processes
between iron and oxygen, takes place.
Writing Ionic Equations Combination Reactions
Precipitation Reactions Decomposition Reactions We lay the groundwork for reaction
Acid-Base Reactions Displacement Reactions classes in this chapter and revisit their
4.3 Oxidation-Reduction (Redox) 4.5 Reversible Reactions: An endless variety throughout the text.
Reactions Introduction to Chemical Equilibrium
Forming Ionic and Covalent Compounds
Redox Terminology
Concepts and he amazing variety that we see in nature is largely a consequence of
Skills to Review
before you study this chapter
T the amazing variety of chemical reactions. Rapid chemical changes
occur among gas molecules as sunlight bathes the atmosphere or light-
ning rips through a stormy sky (see margin). Oceans are gigantic containers
names and formulas of compounds in which aqueous reaction chemistry goes on unceasingly. In every cell of
(Section 2.8)
your body, thousands of reactions are taking place right now.
nature of ionic and covalent bonding
(Section 2.7) Of the millions of chemical reactions occurring in and around you, we
mole-mass-number conversions have examined only a tiny fraction so far, and it would be impossible to
(Section 3.1) examine them all. Fortunately, it isnt necessary to catalog every reaction,
molarity and mole-volume conver- because when we survey even a small percentage of them, a few major pat-
sions (Section 3.5)
terns of chemical change emerge.
balancing chemical equations (Sec-
tion 3.3) In this chapter, we examine the underlying nature of the three most com-
calculating the amounts of reactants mon reaction processes. Since one of our main themes is aqueous reaction chem-
and products (Section 3.4) istry, we first investigate the crucial role water plays as a solvent for many
reactions. Using those ideas, we then focus on two of these major processes
precipitation and acid-baseexamining why they occur and describing the
use of ionic equations to depict them. Next, we discuss the nature of the third
processoxidation-reductionperhaps the most important of
all. Then, we classify reactions by their change in numbers of
reactants and products and see how these classes overlap with
the three reaction processes. The chapter ends with an intro-
ductory look at the reversible nature of all chemical reactions.

4.1 The Role of Water as a Solvent

Many reactions take place in an aqueous environment, and
our first step toward comprehending them is to understand
how water acts as a solvent. The role a solvent plays in a reac-
tion depends on its chemical nature. Some solvents play a pas-
sive role. They disperse the substances into individual mole-
cules but do not interact with them in other ways. Water plays
a much more active role. It interacts strongly with the reac-
tants and, in some cases, even affects their bonds. Water is
crucial to many chemical and physical processes, and we will
discuss its properties frequently in the text.

The Solubility of Ionic Compounds

When water dissolves an ionic solid, such as potassium bromide (KBr), an
important change occurs. Figure 4.1 shows this change with a simple appa-
ratus that measures electrical conductivity, the flow of electric current. When
the electrodes are immersed in pure water or pushed into solid KBr, no cur-
rent flows. In the aqueous KBr solution, however, a significant current flows,
as shown by the brightly lit bulb. The current flow in the solution implies
the movement of charged particles: when KBr dissolves in water, the K and Br
ions in the solid separate from each other (dissociate) and move toward the
electrode whose charge is opposite the ions charge. A substance that con-
ducts a current when dissolved in water is an electrolyte. Soluble ionic com-
pounds dissociate completely and create a large current, so they are called
strong electrolytes.
As the KBr dissolves, each ion becomes solvated, surrounded by solvent
molecules. We express this dissociation into solvated ions as follows:
H2O
KBr(s) K(aq) Br(aq)
The H2O above the arrow indicates that water is required but is not a reac-
tant in the usual sense. When any water-soluble ionic compound dissolves,
134 the oppositely charged ions separate from each other, become surrounded by water
4.1 The Role of Water as a Solvent 135

+
+
+
+ +
+
+ + +
+
+ +
+ +
+ +
+ +
+ + +
+ +
+ +
+
+ +
+
+ +
+ + +
+ + To (+) To ()
+ electrode electrode

A Distilled water does not B Positive and negative ions C In solution, positive and
conduct a current fixed in a solid do not negative ions move and
conduct a current conduct a current

Figure 4.1 The electrical con-

ductivity of ionic solutions.
molecules, and move throughout the solution. The formula of the compound tells A, When electrodes connected to a
power source are placed in distilled
us the number of moles of different ions that result when the compound
water, no current flows and the bulb is
dissolves. Thus, 1 mol KBr dissociates into 2 mol of ions, 1 mol K and unlit. B, A solid ionic compound, such
1 mol Br. as KBr, conducts no current because
the ions are bound tightly together.
C, When KBr dissolves in H2O, the ions
Sample Problem 4.1 Determining Moles of Ions in Aqueous Ionic separate and move through the solu-
Solutions tion, thereby conducting a current.

PROBLEM How many moles of each ion are in the following solutions?
(a) 5.0 mol ammonium sulfate dissolved in water
(b) 78.5 g cesium bromide dissolved in water
(c) 7.421022 formula units copper(II) nitrate dissolved in water
(d) 35 mL of 0.84 M zinc chloride
PLAN We write an equation that shows the numbers of moles of ions released
when 1 mol of compound dissolves. In (a), we multiply the moles of ions released
by 5.0. In (b), we first convert grams to moles. In (c), we first convert formula
units to moles. In (d), we first convert molarity and volume to moles.
H2O
SOLUTION (a) (NH4)2SO4(s) 2NH4(aq) SO42(aq)
Remember that polyatomic ions remain as intact units in solution.
Calculating moles of NH4 ions:
2 mol NH4
Moles of NH4 5.0 mol (NH4)2SO4 10. mol NH4
1 mol (NH4)2SO4
5.0 mol SO42 is also present.
136 Chapter 4 The Major Classes of Chemical Reactions

H O
(b) CsBr(s) 2
Cs(aq) Br(aq)
Converting from grams to moles:
1 mol CsBr
Moles of CsBr 78.5 g CsBr 0.369 mol CsBr
212.8 g CsBr
Thus, 0.369 mol Cs and 0.369 mol Br are present.
H O
(c) Cu(NO3)2(s) 2
Cu2(aq) 2NO3(aq)
Converting from formula units to moles:
Moles of Cu(NO3)2 7.421022 formula units Cu(NO3)2
1 mol Cu(NO3)2

6.0221023 formula units Cu(NO3)2
0.123 mol Cu(NO3)2
2 mol NO3
A
Moles of NO3 0.123 mol Cu(NO3)2
1 mol Cu(NO3)2
0.246 mol NO3
2
0.123 mol Cu is also present.
(d) ZnCl2(aq) Zn2(aq) 2Cl(aq)
Converting from liters to moles:
1L 0.84 mol ZnCl2
Moles of ZnCl2 35 mL 2.9102 mol ZnCl2
B 103 mL 1L
+ +
2 mol Cl
Moles of Cl 2.9102 mol ZnCl2 5.8102 mol Cl
1 mol ZnCl2
2.9102 mol Zn2 is also present.
CHECK After you round off to check the math, see if the relative moles of ions are
consistent with the formula. For instance, in (a), 10 mol NH4/5.0 mol SO42
+ + 2 NH4/1 SO42, or (NH4)2SO4. In (d), 0.029 mol Zn2/0.058 mol Cl
1 Zn2/2 Cl, or ZnCl2.
C
Follow-up Problem 4.1 How many moles of each ion are in each of the
following solutions?
(a) 2 mol potassium perchlorate dissolved in water
(b) 354 g magnesium acetate dissolved in water
(c) 1.881024 formula units of ammonium chromate dissolved in water
(d) 1.32 L of 0.55 M sodium bisulfate

D +

The Polar Nature of Water

Figure 4.2 Electron distribu-
tion in molecules of H2 and H2O.
Water separates ions in a process that greatly reduces the electrostatic force of
A, In H2, the nuclei are identical, so they attraction between them. To see how it does this, lets examine the water
attract the electrons equally. Note that molecule closely. Waters power as an ionizing solvent results from two fea-
the pair of red dots lies equidistant tures of the water molecule: the distribution of its bonding electrons and its over-
between the nuclei, so electron density all shape.
is balanced (light gray). B, In H2O, the O
nucleus attracts the shared electrons
Recall from Section 2.7 that the electrons in a covalent bond are shared
more strongly than the H nucleus, between the bonded atoms. In a covalent bond that exists between identical
creating an uneven charge distribution atoms (as in H2, Cl2, and O2), the sharing is equal. As Figure 4.2A shows,
in each bond (shading). The partially the shared electrons in H2 are distributed equally, so no imbalance of charge
negative O end is designated and appears. On the other hand, in covalent bonds between nonidentical atoms,
the partially positive H end is desig-
nated . Note the regions of greater
the sharing is unequal: one atom attracts the electron pair more strongly than
(red) and lesser (blue) electron density. the other. For reasons that well discuss in Chapter 9, the O atom attracts
C, In this ball-and-stick model of H2O, a electrons more strongly than the H atom. Therefore, in each of the OH
polar arrow points to the negative end bonds of water, the electrons spend more time closer to the O, as shown in
of each OH bond. D, The two polar Figure 4.2B. This unequal distribution of the electron pairs negative charge
OH bonds and the bent molecular
shape give rise to the polar H2O mole-
creates partially charged poles at the ends of each OH bond. The O end
cule, with the partially positive end acts as a slightly negative pole (represented by the red shading and the ),
located between the two H atoms. and the H end acts as a slightly positive pole (represented by the blue shad-
4.1 The Role of Water as a Solvent 137

ing and the ). In Figure 4.2C, the bonds polarity is indicated by a polar
arrow (the arrowhead points to the negative pole and the tail is crossed to
make a plus). The partial charges on the O and H atoms in water are much
less than full ionic charges. In KBr, for instance, the electron has been trans-
ferred from the K atom to the Br atom and two ions form. In the polar OH
bond, no ions exist; the electrons have just shifted their average position
nearer to the O atom.
The water molecule also has a bent shape: the HOH atoms form an
angle, not a straight line. The combined effects of its bent shape and its polar
bonds make water a polar molecule. As you can see in Figure 4.2D, the O
portion of the molecule is the partially negative pole, and the region midway
between the H atoms is the partially positive pole.

Ionic Compounds in Water With these bent, polar water molecules in mind, Solid Solvents for Ions
imagine a granule of an ionic compound in water. Figure 4.3 shows water Because of its partial charges,
molecules congregating over the orderly array of ions at the granules sur- water is an excellent liquid solvent
face; the negative ends of some are attracted to the cations, and the positive for ionic species, but some solids
behave in a similar way. For
ends of others are attracted to the anions. An electrostatic tug of war occurs
example, poly(ethylene oxide) is a
as the ions become partially solvated. The attraction between each ion and
polymer with a repeating structure
water molecules gradually replaces the attraction of the oppositely charged written as
ions for each other. As a result, the ions become completely solvated, sepa- H H
rate from one another, and move randomly throughout the solution. A sim- O
C C
ilar scene occurs whenever an ionic compound dissolves in water. n
Although many ionic compounds dissolve in water, many others do not. H H
In such cases, the electrostatic attraction among ions in the compound is where the n indicates many
greater that the attraction between ions and water molecules, so the sub- identical groups linked covalently
stance remains intact. Actually, these so-called insoluble substances do dis- together. The partial negative
solve to a very small extent, usually several orders of magnitude less than charges on the oxygen atoms can
surround metal cations, such as
so-called soluble substances. Compare, for example, the solubilities of NaCl
Li, and solvate them while
(a soluble compound) and AgCl (an insoluble compound):
remaining in the solid state.
Solubility of NaCl in H2O at 20C 365 g/L Poly(ethylene oxide) and related
Solubility of AgCl in H2O at 20C 0.009 g/L polymers are essential parts of the
lithium-ion batteries used in laptop
In Chapter 13, we examine the factors that influence solubility quantitatively, computers and other portable
but the simple distinction between soluble and insoluble is useful for our electronic devices.
purposes in this chapter.

Figure 4.3 The dissolution of

an ionic compound. When an ionic
compound dissolves in water, H2O
molecules separate, surround, and
disperse the ions into the liquid. Note
that the negative ends of the H2O mole-
cules face the positive ions and the
positive ends face the negative ions.

+
+

+
+
+ +

+
+


138 Chapter 4 The Major Classes of Chemical Reactions

Covalent Compounds in Water Water dissolves many covalent substances

also. Table sugar (sucrose, C12H22O11), beverage (grain) alcohol (ethanol,
C2H6O), and automobile antifreeze (ethylene glycol, C2H6O2) are some famil-
iar examples. All contain their own polar OH bonds, which interact with
those of water. However, even though these substances dissolve, they do not
dissociate into ions but remain as intact molecules. Since their aqueous solutions
do not conduct an electric current, these substances are called nonelec-
trolytes. Many other covalent substances, such as benzene (C6H6) and
octane (C8H18), do not contain polar bonds, and these substances do not dis-
solve appreciably in water.
A small, but very important, group of H-containing covalent molecules
interacts so strongly with water that their molecules do dissociate into ions.
In aqueous solution, they are all acids, as youll see shortly. The molecules
contain polar bonds to hydrogen, such that the atom bonded to H pulls more
strongly on the shared electron pair. A good example is hydrogen chloride
gas. The Cl end of the HCl molecule is partially negative, and the H end is
partially positive. When HCl dissolves in water, the partially charged poles of
H2O molecules are attracted to the oppositely charged poles of HCl. The HCl
bond breaks, with the H becoming the solvated cation H(aq) and the Cl
becoming the solvated anion Cl(aq). Hydrogen bromide behaves similarly
when it dissolves in water:
H O
HBr(g) 2 H(aq) Br(aq)

Sample Problem 4.2 Determining the Molarity of H Ions in Aqueous

Solutions of Acids
PROBLEM Nitric acid is a major chemical in the fertilizer and explosives industries.
In aqueous solution, each molecule dissociates and the H becomes a solvated H
ion. What is the molarity of H(aq) in 1.4 M nitric acid?
PLAN The molarity of acid is given, so we determine the formula to find the num-
ber of moles of H(aq) present in 1 L solution.
SOLUTION Nitrate ion is NO3, so nitric acid is HNO3. Thus, 1 mol H(aq) is
released per mole of acid:
H2O
H(aq) NO3(aq)
HNO3(l)
Therefore, 1.4 M HNO3 contains 1.4 mol H(aq)/L, or 1.4 M H(aq).

Follow-up Problem 4.2 How many moles of H(aq) are present in 451 mL
of 3.20 M hydrobromic acid?
+
The solvated hydrogen cation, H(aq), is an unusual species. The H atom
is a proton surrounded by an electron, so the H ion is just a proton. Because
its positive charge is concentrated in such a tiny volume, H attracts the neg-
H3O+ ative pole of surrounding water molecules very strongly and actually forms
a covalent bond to one of the molecules. This fact is indicated by writing the
Figure 4.4 The hydrated proton. aqueous H ion as H3O (hydronium ion), but to make a point here, we
The charge of the H ion is highly con- write it as (H2O)H. The hydronium ion associates tightly with other water
centrated because the ion is so small. In molecules in a mixture that includes H5O2 [or (H2O)2H], H7O3 [or
aqueous solution, it forms a covalent (H2O)3H], H9O4 [or (H2O)4H], and still larger aggregates; H7O3 is shown
bond to a water molecule and exists as
an H3O ion associated tightly with
in Figure 4.4. These various forms exist together, but H(aq) is often used as
other H2O molecules. Here, the H7O3 a general, simplified notation. Later, to emphasize the role of water, we show
ion is shown. the solvated proton as H3O(aq).
4.2 Precipitation Reactions and Acid-Base Reactions 139

Section Summary
When an ionic compound dissolves in water, the ions dissociate and are sol-
vated by water molecules. Because the ions are free to move, their solutions
conduct electricity. Water plays an active role in dissolving ionic compounds
because it consists of polar molecules that are attracted to the ions. Water
also dissolves many covalent substances, and it interacts with some H-con-
taining molecules so strongly that it breaks covalent bonds and dissociates
them into H(aq) ions and anions.

4.2 Precipitation Reactions and Acid-Base Reactions

Of the many thousands of reactions that occur in the environment and in
organisms, the overwhelming majority take place in aqueous solution. In this
section, we focus on two of the three most important reaction processes
precipitation and acid-base. We begin by asking why these reactions occur and
how to write equations that depict the essential chemical change.

The Driving Force for Many Aqueous Ionic Reactions

Because aqueous ionic reactions are so common, you may think that a reac-
tion occurs whenever solutions of two ionic compounds are mixed, but that
is not the case. What drives an aqueous ionic reaction to occur? In many
cases, particularly for precipitation and acid-base processes, a reaction occurs
because certain ions attract each other so strongly that they are removed from solution
in formation of the product. Consider this example. Prepare separate solutions
of sodium iodide and potassium nitrate, and their ions disperse throughout
the solutions:
H2O
Na(aq) I(aq)
NaI(s)
H2O
K(aq) NO3(aq)
KNO3(s)
If you mix these solutions, does a reaction occur? In order to decide, you must
examine the ion combinations to see if any of the possible products are insoluble, that
is, do not dissociate into ions. In other words, you must see if ions are removed
from solution. The reactant ions are
Na(aq) I(aq) K(aq) NO3(aq) ?
In addition to the two original reactants, NaI and KNO3, which you know
are soluble, the possible cation-anion combinations are NaNO3 and KI. In this
case, a reaction does not occur because these two are also soluble ionic com-
pounds. Therefore, the ions just remain in solution. (Youll see shortly how
to determine if a product is soluble.)
Next, you substitute a solution of Pb(NO3)2 for the KNO3, and a yellow
solid forms, as shown in Figure 4.5. In addition to the two soluble reactants,
the possible ion combinations are NaNO3 and PbI2, so the solid must be
lead(II) iodide. In this case, a reaction does occur because ions are removed
from the solution to form PbI2:
2Na(aq) 2I(aq) Pb2(aq) 2NO3(aq) 2Na(aq) 2NO3(aq) PbI2(s)
Writing Ionic Equations for Aqueous Ionic Reactions
Chemists write three types of equations to represent aqueous ionic reactions:
molecular, total ionic, and net ionic equations. In ionic equations, atoms and Figure 4.5 The reaction of
charges must balance; as youll see, by balancing the atoms, we balance the Pb(NO3)2 and NaI. When aqueous
charges also. Lets examine a reaction to see what each of these equations solutions of these ionic compounds are
shows. When solutions of silver nitrate and sodium chromate are mixed, the mixed, the yellow solid PbI2 forms.
140 Chapter 4 The Major Classes of Chemical Reactions

Figure 4.6 A precipitation

reaction and its equations. When
silver nitrate and sodium chromate
solutions are mixed, a reaction occurs
that forms solid silver chromate and a
solution of sodium nitrate. The photos
(top) present the macroscopic view of
the reaction, the view the chemist sees
in the lab. The blow-up arrows lead to
an atomic-scale view (middle), a repre-
sentation of the chemists mental pic-
ture of the reactants and products. (The
pale ions are spectator ions, present for
electrical neutrality, but not involved in
the reaction.) Three equations represent
NO3
the reaction in symbols. The molecular CrO42
equation shows all substances intact.
The total ionic equation shows all solu- Na+
ble substances as separate, solvated
ions. The net ionic equation eliminates Ag+
the spectator ions to show only the
reacting species. +

Molecular equation
2AgNO3(aq) + Na2CrO4(aq) Ag2CrO4(s) + 2NaNO3(aq)
Silver nitrate Sodium chromate Silver chromate Sodium nitrate

Total ionic equation

2Ag+(aq) + 2NO3(aq) + 2Na+(aq) + CrO42(aq) Ag2CrO4(s) + 2Na+(aq)
+ 2NO3(aq)

Net ionic equation

2Ag+(aq) + CrO42(aq) Ag2CrO4(s)

brick-red solid silver chromate (Ag2CrO4) forms. Figure 4.6 depicts the
change you would see if you mixed these solutions in the lab, how you might
imagine the change at the atomic level among the ions, and how you can
symbolize the change with the three types of ionic equations.
The molecular equation (top) reveals the least about the actual change
because the reactants and products are written as if they were intact, undissociated
compounds:
2AgNO3(aq) Na2CrO4(aq) Ag2CrO4(s) 2NaNO3(aq)
The total ionic equation (middle) shows the reaction more realistically
because all the soluble ionic substances are dissociated into ions. Now the
Ag2CrO4(s) stands out as the only undissociated substance:
2Ag(aq) 2NO3(aq) 2Na(aq) CrO42(aq)
Ag2CrO4(s) 2Na(aq) 2NO3(aq)
Notice that the Na(aq) and NO3(aq) ions are unchanged in the equation.
They are called spectator ions because they are not involved in the actual
chemical change. These ions are present as part of the reactants. In other
words, we could not have added Ag ions without also adding an anion, in
this case NO3 ion.
The net ionic equation (bottom) eliminates the spectator ions to show the
actual chemical change taking place:
2Ag(aq) CrO42(aq) Ag2CrO4(s)
4.2 Precipitation Reactions and Acid-Base Reactions 141

Table 4.1 Solubility Rules for Ionic Compounds in Water

Soluble Ionic Compounds Insoluble Ionic Compounds

1. All common compounds of Group 1A(1) ions (Li , Na , 1. All common metal hydroxides are insoluble, except those
K, etc.) and ammonium ion (NH4) are soluble. of Group 1A(1) and the larger members of Group 2A(2)
2. All common nitrates (NO3), acetates (CH3COO), and (beginning with Ca2).
most perchlorates (ClO4) are soluble. 2. All common carbonates (CO32) and phosphates (PO43)
3. All common chlorides (Cl), bromides (Br), and are insoluble, except those of Group 1A(1) and NH4.
iodides (I) are soluble, except those of Ag, Pb2, Cu, 3. All common sulfides are insoluble except those of Group
and Hg22. 1A(1), Group 2A(2), and NH4.
4. All common sulfates (SO42) are soluble, except those of
Ca2, Sr2, Ba2, and Pb2.

The formation of solid silver chromate from silver ions and chromate ions is
the only change. In fact, if we had originally mixed solutions of potassium
chromate, K2CrO4(aq), and silver acetate, AgC2H3O2(aq), the same change
would have occurred. Only the spectator ions would differK(aq) and
C2H3O2(aq) instead of Na(aq) and NO3(aq). Thus, writing the net ionic
equation is an excellent way to isolate the key chemical event.

Precipitation Reactions
In precipitation reactions, two soluble ionic compounds react to form an
insoluble product, a precipitate. The two reactions that you just saw
between lead(II) nitrate and sodium iodide and between silver nitrate and
sodium chromate are examples. Precipitates form for the same reason that
some ionic compounds do not dissolve: the electrostatic attraction between
the ions of the precipitate outweighs the tendency of the ions to become sol-
vated and move randomly throughout the solution. When solutions of such
ions are mixed, the ions collide and stay together, and the resulting substance
comes out of solution as a solid. As youve seen, if all the ions remain in
solution, no reaction occurs, but if ions precipitate, a reaction does occur.
Thus, the event that drives a precipitation reaction to occur is the mutual
attraction between ions and their removal from solution in the form of an insoluble
ionic compound.
How can we predict whether a precipitate will form when we mix aque-
ous solutions of two ionic compounds? As you saw above, three steps are
involved:
1. Note the ions present in the reactants.
2. Consider the possible cation-anion combinations.
3. Predict whether any of the combinations is insoluble.
A difficulty arises immediately with the last step because there is no simple
way to predict solubility. Instead, you must memorize the short list of solu-
bility rules shown in Table 4.1. These rules dont cover every possible ionic
compound, but learning them allows you to predict the outcome of a great
number of precipitation reactions.

Sample Problem 4.3 Predicting Whether a Precipitation Reaction Occurs;

Writing Ionic Equations
PROBLEM Predict whether a reaction occurs when each of the following pairs of
solutions are mixed. If a reaction does occur, write balanced molecular, total ionic,
and net ionic equations, and identify the spectator ions.
(a) Sodium sulfate(aq) strontium nitrate(aq)
(b) Ammonium perchlorate(aq) sodium bromide(aq)
142 Chapter 4 The Major Classes of Chemical Reactions

PLAN For each pair of solutions, we note the ions present in the reactants, write
the cation-anion combinations, and refer to Table 4.1 to see if any are insoluble.
For the molecular equation, we predict the products. For the total ionic equation,
we write the soluble compounds as separate ions. For the net ionic equation, we
eliminate the spectator ions.
SOLUTION (a) In addition to the reactants, the two other ion combinations are
strontium sulfate and sodium nitrate. Table 4.1 shows that strontium sulfate is
insoluble, so a reaction does occur. Writing the molecular equation:
Na2SO4(aq) Sr(NO3)2(aq) SrSO4(s) 2NaNO3(aq)
Writing the total ionic equation:
2Na(aq) SO42(aq) Sr2(aq) 2NO3(aq)
SrSO4(s) 2Na(aq) 2NO3(aq)
Writing the net ionic equation:
Sr2(aq) SO42(aq) SrSO4(s)
The spectator ions are Na and NO3.
(b) The other ion combinations are ammonium bromide and sodium perchlorate.
Table 4.1 shows that all ammonium, sodium, and most perchlorate compounds are
soluble, and all bromides are soluble except those of Ag, Pb2, Cu, and Hg22.
Therefore, no reaction occurs. The compounds remain dissociated in solution as
solvated ions.
Follow-up Problem 4.3 Predict whether a reaction occurs, and write bal-
anced total and net ionic equations:
(a) Iron(III) chloride(aq) cesium phosphate(aq)
(b) Sodium hydroxide(aq) cadmium nitrate(aq)
(c) Magnesium bromide(aq) potassium acetate(aq)
(d) Silver sulfate(aq) barium chloride(aq)

Acid-Base Reactions
Aqueous acid-base reactions involve water not only as solvent but also in the
more active roles of reactant and product. These reactions are the essential
chemical events in processes as diverse as the biochemical synthesis of pro-
teins, the industrial production of several fertilizers, and some of the pro-
Figure 4.7 The behavior of
strong and weak electrolytes. posed methods for revitalizing lakes damaged by acid rain.
A, Strong electrolytes include soluble Obviously, an acid-base reaction (also called a neutralization reaction)
ionic compounds, strong acids, and occurs when an acid reacts with a base, but the definitions of these terms
strong bases. They dissociate com- and the scope of this reaction process have changed considerably over the
pletely into ions, so they conduct a
years. For our purposes at this point, well use definitions proposed by the
large current. B, Weak electrolytes
include weak acids and weak bases. great Swedish chemist Svante Arrhenius,
They dissociate only partially into ions, An acid is a substance that produces H ions when dissolved in water.
so they conduct a small current. A base is a substance that produces OH ions when dissolved in water.
(Other definitions of acid and base are presented later in this sec-
tion and again in Chapter 18, along with a fuller meaning of neu-
tralization.) Acids and bases are the active ingredients in many
everyday products: most drain, window, and oven cleaners con-
tain bases; vinegar and lemon juice contain acids.
Acids and bases are electrolytes and are often categorized in
terms of strength, which refers to their degree of dissociation
into ions in aqueous solution. Strong acids and strong bases dissociate
completely into ions when they dissolve in water. Therefore, like
soluble ionic compounds, they are strong electrolytes. In contrast,
weak acids and weak bases dissociate so little that most of their molecules
remain intact. As a result, they conduct a small current, as shown
in Figure 4.7, and are weak electrolytes. Table 4.2 lists some labo-
A Strong electrolyte B Weak electrolyte ratory acids and bases in terms of their strength.
4.2 Precipitation Reactions and Acid-Base Reactions 143

Both strong and weak acids have one or more H atoms as part of their
structure. Strong bases have either the OH or the O2 ion as part of their Table 4.2 Selected Acids
structure. Soluble ionic oxides, such as K2O, act as strong bases because the and Bases
oxide ion reacts with water to form hydroxide ion: Acids
O2(aq) H2O(l) 2OH(aq)
Strong
Weak bases, such as ammonia, do not contain OH ions, but they produce Hydrochloric acid, HCl
them in a reaction with water that occurs to a small extent: Hydrobromic acid, HBr
NH3(g) H2O(l) A NH4(aq) OH(aq)
B Hydriodic acid, HI
Nitric acid, HNO3
(Note the reaction arrow in the preceding equation. This type of arrow indi- Sulfuric acid, H2SO4
cates that the reaction proceeds in both directions; well discuss this impor- Perchloric acid, HClO4
tant idea further in Section 4.5.)
Weak
The Net Change: Formation of H2O from H and OH. Lets use ionic equa-
Hydrofluoric acid, HF
tions to examine acid-base reactions. We begin with the molecular equation
Phosphoric acid, H3PO4
for the reaction between the strong acid HCl and the strong base Ba(OH)2: Acetic acid, CH3COOH
2HCl(aq) Ba(OH)2(aq) BaCl2(aq) 2H2O(l) (or HC2H3O2)
Since HCl and Ba(OH)2 dissociate completely and H2O remains undissociated, Bases
the total ionic equation is
Strong
2H(aq) 2Cl(aq) Ba2(aq) 2OH(aq) Ba2(aq) 2Cl(aq) 2H2O(l) Sodium hydroxide, NaOH
Note the removal of ions to form H2O. In the net ionic equation, we eliminate Potassium hydroxide, KOH
the spectator ions Ba2(aq) and Cl(aq) and see the actual reaction: Calcium hydroxide, Ca(OH)2
Strontium hydroxide, Sr(OH)2
2H(aq) 2OH(aq) 2H2O(l) or H(aq) OH(aq) H2O(l) Barium hydroxide, Ba(OH)2
Thus, the essential chemical change in all aqueous reactions between strong acids and
strong bases is that an H ion from the acid and an OH ion from the base form a Weak
water molecule; only the spectator ions differ from one reaction to another. Ammonia, NH3
A key point to note is that, like precipitation reactions, acid-base reactions
are driven by the electrostatic attraction of ions and their removal from solution in
the formation of the product. In this case, the ions are H and OH and the
product is H2O, which consists almost entirely of undissociated molecules.
(Actually, water molecules dissociate very slightly, as youll see in later chap-
ters, but the formation of water in a neutralization reaction represents an
enormous net removal of H and OH ions.)
If we evaporate the water from the above reaction mixture, the ionic solid
barium chloride remains. An ionic compound that results from the reaction
of an acid and a base is called a salt. Thus, in a typical aqueous neutraliza-
tion reaction, the reactants are an acid and a base, and the products are a salt and
water:
HX(aq) MOH(aq) MX(aq) H2O(l)
acid base salt water

Note that the cation of the salt comes from the base and the anion comes from the
acid.

Sample Problem 4.4 Writing Ionic Equations for Acid-Base Reactions

PROBLEM Write balanced molecular, total ionic, and net ionic equations for each of
the following acid-base reactions and identify the spectator ions:
(a) Strontium hydroxide(aq) perchloric acid(aq)
(b) Barium hydroxide(aq) sulfuric acid(aq)
PLAN All are strong acids and bases (see Table 4.2), so the essential reaction is
between H and OH. The products are H2O and a salt made from the spectator
ions. Note that in (b), the salt (BaSO4) is insoluble (see Table 4.1), so virtually all
ions are removed from solution.
144 Chapter 4 The Major Classes of Chemical Reactions

SOLUTION (a) Writing the molecular equation:

Sr(OH)2(aq) 2HClO4(aq) Sr(ClO4)2(aq) 2H2O(l)
Writing the total ionic equation:
Sr2(aq) 2OH(aq) 2H(aq) 2ClO4(aq)
Sr2(aq) 2ClO4(aq) 2H2O(l)
Writing the net ionic equation:
2OH(aq) 2H(aq) 2H2O(l) or OH(aq) H(aq) H2O(l)
Sr2(aq) and ClO4(aq) are the spectator ions.
(b) Writing the molecular equation:
Ba(OH)2(aq) H2SO4(aq) BaSO4(s) 2H2O(l)
Writing the total ionic equation:
Ba2(aq) 2OH(aq) 2H(aq) SO42(aq) BaSO4(s) 2H2O(l)
The net ionic equation is the same as the total ionic equation. This is a precipita-
tion and a neutralization reaction. There are no spectator ions because all the ions
are used to form the two products.
Follow-up Problem 4.4 Write balanced molecular, total ionic, and net ionic
equations for the reaction between aqueous solutions of calcium hydroxide and
nitric acid.

Acid-Base Titrations Chemists apply stoichiometry to study acid-base reac-

tions quantitatively through a titration. In any titration, one solution of known
concentration is used to determine the concentration of another solution through a mon-
itored reaction. In a typical acid-base titration, a standardized solution of base,
one whose concentration is known, is added slowly to an acid solution of
unknown concentration.
The laboratory procedure is straightforward but requires careful technique,
as shown in Figure 4.8. A known volume of the acid solution is placed in a
flask, and a few drops of indicator solution are added. An acid-base indi-

Figure 4.8 An acid-base titra-

tion. A, In this procedure, a measured
volume of the unknown acid solution is
placed in a flask beneath a buret con-
taining the known (standardized) base
solution. A few drops of indicator are
added to the flask; the indicator used
here is phenolphthalein, which is color-
less in acid and pink in base. After an
initial buret reading, base (OH ions) is
added slowly to the acid (H ions).
B, Near the end of the titration, the
indicator momentarily changes to its
base color but reverts to its acid color
with swirling. C, When the end point is
reached, a tiny excess of OH is pres-
ent, shown by the permanent change in
A B C
color of the indicator. The difference
between the final buret reading and the
initial buret reading gives the volume of H+(aq ) + X(aq ) + M+(aq ) + OH(aq ) H2O(l ) + M+(aq ) + X(aq )
base used.
4.2 Precipitation Reactions and Acid-Base Reactions 145

cator is a substance whose color is different in acid than in base. (In Chap-
ter 18 we examine indicators more fully.) The standardized solution of base
is added slowly from a buret clamped above the flask. As the titration nears
its end, indicator molecules change color near a drop of added base due to
the temporary excess of OH ions there. As soon as the solution is swirled,
however, the indicators acidic color returns. The equivalence point in the
titration occurs when all the moles of H ions present in the original volume of acid
solution have reacted with an equivalent number of moles of OH ions added from
the buret:
Moles of H (originally in flask) moles of OH (added from buret)
The end point of the titration occurs when a tiny excess of OH ions
changes the indicator permanently to its color in base. In calculations, we
assume this tiny excess is insignificant, and therefore the amount of base needed
to reach the end point is the same as the amount needed to reach the equivalence point.

Sample Problem 4.5 Finding the Concentration of Acid from an

Acid-Base Titration
PROBLEM You perform an acid-base titration to standardize an HCl solution by
placing 50.00 mL HCl in a flask with a few drops of indicator solution. You put
0.1524 M NaOH into the buret and the initial reading is 0.55 mL. At the end point,
the buret reading is 33.87 mL. What is the concentration of the HCl solution?
PLAN We must find the molarity of acid from the volume of acid, the initial and Volume (L) of base
final volumes of base, and the molarity of base. First, we balance the equation. We (difference in buret readings)
find the volume of base added from the difference in buret readings and use its
molarity to calculate the amount (mol) of base added. Then, we use the molar ratio multiply by
from the balanced equation to find the amount (mol) of acid originally present and M (mol/L) of base
divide by its original volume to find the molarity.
SOLUTION Writing the balanced equation: Amount (mol) of base
NaOH(aq) HCl(aq) NaCl(aq) H2O(l)
Finding volume (L) of NaOH solution added: molar ratio

1L
Volume (L) of solution (33.87 mL soln 0.55 mL soln)
1000 mL
Amount (mol) of acid
0.03332 L soln
Finding amount (mol) of NaOH added: divide by
0.1524 mol NaOH volume (L) of acid
Moles of NaOH 0.03332 L soln
1 L soln
5.078103 mol NaOH M (mol/L) of acid

Finding amount (mol) of HCl originally present: Since the molar ratio is 1:1,
1 mol HCl
Moles of HCl 5.078103 mol NaOH 5.078103 mol HCl
1 mol NaOH
Calculating molarity of HCl:
5.078103 mol HCl 1000 mL
Molarity of HCl 0.1016 M HCl
50.00 mL 1L
CHECK The answer seems reasonable because a larger volume of less concentrated
acid neutralized a smaller volume of more concentrated base. Also check that the
moles of H and OH are about equal: 50 mL 0.1 M H+ 0.005 mol 33 mL
0.15 M OH.
Follow-up Problem 4.5 What volume of 0.1292 M Ba(OH)2 would neutral-
ize 50.00 mL of the HCl solution standardized in the sample problem above?
146 Chapter 4 The Major Classes of Chemical Reactions

A Closer Look at Acid-Base Reactions We gain deeper insight into acid-

base reactions if we look more closely at the actual species present in solu-
tion. Lets see what takes place when a substance like HCl gas dissolves in
water. As we discussed earlier, the polar water molecules pull apart the HCl
molecule and the H ion bonds to a water molecule. In essence, we can say
that HCl transfers its proton to H2O:
H transfer

HCl(g) H2O(l) H3O(aq) Cl(aq)

Thus, a solution of hydrochloric acid actually consists of solvated H3O and
solvated Cl ions.
When sodium hydroxide solution is added, the H3O ion transfers a pro-
ton to the OH ion of the base (with the product water shown here as HOH):
H transfer

[H3O (aq) Cl(aq)] [Na(aq) OH(aq)]

H2O(l) Na(aq) Cl(aq) HOH(l)

Without the spectator ions, the transfer of a proton from H3O to OH is
obvious:
H transfer

H3O(aq) OH(aq) H2O(l) HOH(l) [or 2H2O(l)]

Compare this net ionic reaction with the one we saw earlier,
H(aq) OH(aq) H2O(l)
Figure 4.9 An aqueous strong and youll see they are identical (with the additional H2O molecule coming
acidstrong base reaction on the
atomic scale. When solutions of a
from the H3O). Clearly, an acid-base reaction is a proton-transfer process. The
strong acid (HX) and a strong base Na and Cl ions remain in solution, and if the water is evaporated, they
(MOH) are mixed, the H3O from the crystallize as the salt NaCl. Figure 4.9 shows this process on the atomic level.
acid transfers a proton to the OH from
the base to form an H2O molecule.
Evaporation of the water leaves the
spectator ions, X and M, as a solid
ionic compound called a salt.

M+ and X ions
remain in solution
X
as spectator ions

H 3O+

HX(aq ) Evaporation of
Aqueous solutions of M+
strong acid water leaves
strong acid and strong
+ base are mixed
solid salt
Salt crystal
X

M+ +
M X

Chemical change
OH
is transfer of H+
from H 3O+ to OH
MOH(aq ) forming H 2O
strong base

H3O+(aq ) + X (aq )
mix
2H2O(l ) + M+(aq ) + X (aq )

+ 2H2O(g) + MX(s)
M+(aq ) + OH (aq )
4.2 Precipitation Reactions and Acid-Base Reactions 147

In the early 20th century, the chemists Johannes Brnsted and Thomas
Lowry realized the proton-transfer nature of acid-base reactions. They defined
an acid as a molecule (or ion) that donates a proton, and a base as a molecule (or
ion) that accepts a proton. Therefore, in the aqueous reaction between strong
acid and strong base, H3O ion acts as the acid and OH ion acts as the base.
Because they ionize completely, a given amount of strong acid (or strong
base) creates an equivalent amount of H3O (or OH) when it dissolves in
water. (We discuss the Brnsted-Lowry concept thoroughly in Chapter 18.)
Acid-Base Reactions That Form a Gaseous Product Thinking of acid-base
reactions as proton-transfer processes helps us understand another common
type of aqueous ionic reaction, those that form a gaseous product. For exam-
ple, when an ionic carbonate, such as K2CO3, is treated with an acid, such
as HCl, one of the products is carbon dioxide. The driving force for this and sim-
ilar reactions is formation of a gas and water because both products remove reactant
ions from solution:
2HCl(aq) K2CO3(aq) 2KCl(aq) [H2CO3(aq)]
The product H2CO3 is often shown in brackets to indicate that it is very unsta-
ble. It decomposes immediately into water and carbon dioxide:
[H2CO3(aq)] H2O(l) CO2(g)
Combining these gives the overall equation:
2HCl(aq) K2CO3(aq) 2KCl(aq) H2O(l) CO2(g)

When we show H3O ions from the HCl as the actual species in solution
and write the net ionic equation, Cl and K ions are eliminated. Note that
each of the two H3O ions transfers a proton to the carbonate ion:
2H transfer

2H3O(aq) CO32(aq) 2H2O(l) [H2CO3(aq)] 3H2O(l) CO2(g)

In essence, then, this is an acid-base reaction, with carbonate ion accepting
the protons and, therefore, acting as the base.
Several other polyatomic ions act similarly in reaction with acid, as in the
formation of SO2 from ionic sulfites. For a reaction of an ionic sulfite with
strong acid, the net ionic equation is
2H transfer

SO32
(aq) 2H3O(aq) SO2(g) 3H2O(l) Figure 4.10 An acid-base reac-
tion that forms a gaseous prod-
Ionic equations are written differently for the reactions of weak acids. Fig- uct. Carbonates and hydrogen
ure 4.10 shows a household example of the gas-forming reaction between carbonates react with acids to form
vinegar (an aqueous 5% solution of acetic acid) and baking soda (sodium gaseous CO2 and H2O. Here, dilute
hydrogen carbonate) solution. Look closely at the equations. Since acetic acid acetic acid solution (vinegar) is added to
is a weak acid (see Table 4.2), it dissociates very little. To show this, weak sodium hydrogen carbonate (baking
soda) solution and bubbles of CO2 gas
acids appear undissociated in the net ionic equation; note that H3O does not form. (Note that the net ionic equation
appear. Therefore, only Na(aq) is a spectator ion; CH3COO(aq) is not. includes acetic acid because it is a
weak acid and does not dissociate into
ions to an appreciable extent.)

Molecular equation
NaHCO3(aq) + CH3COOH(aq) CH3COONa(aq) + CO2(g) + H2O(l )

Total ionic equation

Na+(aq) + HCO3(aq) + CH3COOH(aq) CH3COO(aq) + Na+(aq) + CO2(g) + H2O(l )

Net ionic equation

HCO3(aq) + CH3COOH(aq) CH3COO(aq) + CO2(g) + H2O(l )
148 Chapter 4 The Major Classes of Chemical Reactions

Section Summary
When solutions of ionic compounds are mixed, a reaction occurs only if a
product forms that removes ions from the solution. A molecular equation
shows reactants and products as undissociated compounds. A total ionic
equation shows soluble ionic compounds (and other strong electrolytes) as
solvated ions. A net ionic equation shows only those species that change dur-
ing the reaction; those that do not change are spectator ions. Precipitation
reactions occur when ions are removed from solution to form an insoluble
ionic compound. Acid-base (neutralization) reactions occur when ions are
removed as an acid (an H-yielding substance) and a base (an OH-yielding
substance) form a water molecule. Strong acids and bases dissociate com-
pletely; weak acids and bases dissociate slightly. In titrations, a known con-
centration of one reactant is used to determine the concentration of the other.
Acid-base reactions can also be viewed as the transfer of a proton from an
acid to a base. An ionic gas-forming reaction is an acid-base reaction in which
an acid transfers a proton to a polyatomic ion (carbonate or sulfite), and a
gas forms that leaves the reaction mixture.

4.3 Oxidation-Reduction (Redox) Reactions

Redox reactions are the third and, perhaps, most important of all chemical
processes. They include the formation of a compound from its elements (and
vice versa), all combustion reactions, the reactions that generate electricity in
batteries, and the production of cellular energy. In this section, we examine
the redox process in detail and learn some essential terminology. We see one
way to balance redox equations and how to apply them quantitatively.

Redox Processes in the Formation of Ionic and

Covalent Compounds
In oxidation-reduction (or redox) reactions, the key chemical event is
the net movement of electrons from one reactant to the other. Such movement
of electron charge occurs in the formation of both ionic and covalent com-
pounds. As an example, lets reconsider the flashbulb reaction (see Figure 3.7,
p. 105), in which an ionic compound, MgO, forms from its elements:
2Mg(s) O2(g) 2MgO(s)
Figure 4.11A shows that during the reaction, each Mg atom loses two elec-
trons and each O atom gains them; that is, two electrons move from each
Mg atom to each O atom. This change represents a transfer of electron charge
away from each Mg atom and toward each O atom, resulting in the forma-
tion of Mg2 and O2 ions. Attractions among the ions form the solid.
During the formation of a covalent compound from its elements, there is
a net movement of electrons also, but it is more of a shift in electron charge
than a transfer, and thus, not enough to form ions. Consider the formation
of HCl gas:
H2(g) Cl2(g) 2HCl(g)
To see the electron movement here, we compare the electron charge distri-
butions in the reactant bonds and in the product bonds. As Figure 4.11B
shows, H2 and Cl2 molecules are each held together by pure covalent bonds;
that is, the electrons are shared equally between the bonded atoms. In the
HCl molecule, the electrons are shared unequally because the Cl atom attracts
them more strongly than the H atom does. Thus, in HCl, the H has less elec-
tron charge (blue shading) than it had in H2, whereas the Cl has more charge
(red shading) than it had in Cl2. In other words, in HCl there has been a shift
of electron charge away from the H atom and toward the Cl atom. Be sure you
4.3 Oxidation-Reduction (Redox) Reactions 149

2e Figure 4.11 The redox process

Mg2+ in compound formation. A, In form-
Transfer of ing the ionic compound MgO, each Mg
electrons atom transfers two electrons to each O
+
Mg + O atom. (Note that atoms become smaller
when they lose electrons and larger
when they gain them.) The resulting
O 2
Mg2 and O2 ions aggregate with
A Formation of an ionic compound many others to form an ionic solid. B, In
Ionic solid
the reactants H2 and Cl2, the electron
pairs are shown centrally located to
indicate that they are shared equally. In
+ the covalent compound HCl, the Cl
H H H Cl attracts the shared electron pair more
Shift of
Electron electrons Electron strongly than the H does. In effect, H
pairs shared + pairs shared shifts its electron toward Cl. Note the
equally unequally polar nature of the HCl molecule, as
+ shown by higher electron density (red)
Cl Cl H Cl near the Cl end and lower electron
density (blue) near the H end.

B Formation of a covalent compound

realize that this electron shift is not nearly as extreme as the electron trans-
fer during MgO formation. In fact, in some cases, the net movement of elec-
trons is slight but still constitutes a redox reaction.

Some Essential Redox Terminology

Chemists use some important terminology to describe the movement of elec-
trons that occurs in oxidation-reduction reactions. Oxidation is the loss of
electrons, and reduction is the gain of electrons. (The original meaning of
reduction comes from the process of reducing large amounts of metal ore to
smaller amounts of metal, but youll see shortly why we use the term for the
act of gaining.) Thus, during the formation of magnesium oxide, Mg under-
goes oxidation (electron loss) and O2 undergoes reduction (electron gain).
The loss and gain are simultaneous, but we can imagine them occurring in
separate steps:
Oxidation (electron loss by Mg): Mg Mg2 2e

2 O2 2e
1
Reduction (electron gain by O2): O2
Since O2 gained the electrons that Mg lost when it was oxidized, we say
that O2 oxidized Mg. Thus, O2 is the oxidizing agent, the species doing the
oxidizing. Similarly, since Mg gave up the electrons that O2 gained when it
was reduced, we say that Mg reduced O2. Thus, Mg is the reducing agent,
the species doing the reducing.
Once this relationship is clear, you will realize that the oxidizing agent
becomes reduced because it removes the electrons (and thus gains them),
whereas the reducing agent becomes oxidized because it gives up the electrons
(and thus loses them). In the formation of HCl, Cl2 oxidizes H2 (H loses some
electron charge and Cl gains it), which is the same as saying that H2 reduces
Cl2. The reducing agent, H2, is oxidized and the oxidizing agent, Cl2, is
reduced.

Using Oxidation Numbers to Monitor the Movement of

Electron Charge
Chemists have devised a useful bookkeeping system to monitor which atom
loses electron charge and which atom gains it. Each atom in a molecule (or
ionic compound) is assigned an oxidation number (O.N.), or oxidation state,
150 Chapter 4 The Major Classes of Chemical Reactions

Table 4.3 Rules for Assigning an Oxidation Number (O.N.)

General rules
1. For an atom in its elemental form (Na, O2, Cl2, etc.): O.N. 0
2. For a monatomic ion: O.N. ion charge
3. The sum of O.N. values for the atoms in a compound equals zero. The sum of O.N.
values for the atoms in a polyatomic ion equals the ion charge.

Rules for specific atoms or periodic table groups

1. For Group 1A(1): O.N. 1 in all compounds
2. For Group 2A(2): O.N. 2 in all compounds
3. For hydrogen: O.N. 1 in combination with nonmetals
O.N. 1 in combination with metals and boron
4. For fluorine: O.N. 1 in all compounds
5. For oxygen: O.N. 1 in peroxides
O.N. 2 in all other compounds (except with F)
6. For Group 7A(17): O.N. 1 in combination with metals, nonmetals (except O),
and other halogens lower in the group

the charge the atom would have if electrons were not shared but were trans-
ferred completely. Oxidation numbers are determined by the set of rules in
Table 4.3. [Note that an oxidation number has the sign before the number
(2), whereas an ionic charge has the sign after the number (2).]

Sample Problem 4.6 Determining the Oxidation Number of an Element

PROBLEM Determine the oxidation number (O.N.) of each element in the following
+1
1 compounds:
H
Group number (a) Zinc chloride (b) Sulfur trioxide (c) Nitric acid
1
Highest O.N./Lowest O.N. PLAN We apply Table 4.3, especially noting the general rules that the O.N. values
1A 2A 3A 4A 5A 6A 7A in a compound add up to zero, and the O.N. values in a polyatomic ion add up to
+1 +2 +3 +4 4 +5 3 +6 2 +7 1 the ions charge.
Li Be B C N O F SOLUTION (a) ZnCl2. The sum of O.N.s for the monatomic ions in the compound
2
must equal zero. The O.N. of the Zn2 ion is 2. The O.N. of each Cl ion is
3 Na Mg Al Si P S Cl 1, for a total of 2.
(b) SO3. The O.N. of each oxygen is 2, for a total of 6. Since the O.N.s
4 K Ca Ga Ge As Se Br must add up to zero, the O.N. of S is 6.
Period

(c) HNO3. The O.N. of H is 1, so the O.N.s of the NO3 group must add up to
5 Rb Sr In Sn Sb Te I
1 to give zero for the compound. The O.N. of each O is 2 for a total of 6.
6 Cs Ba Tl Pb Bi Po At Therefore, the O.N. of N is 5.
Follow-up Problem 4.6 Determine the O.N. of each element in the follow-
7 Fr Ra
ing: (a) scandium oxide (Sc2O3); (b) gallium chloride (GaCl3); (c) hydrogen phos-
phate ion; (d) iodine trifluoride.
Figure 4.12 Highest and lowest
oxidation numbers of reactive
main-group elements. The A-group
number shows the highest possible The periodic table is a great help in learning the highest and lowest oxi-
oxidation number (O.N.) for a main- dation numbers of most main-group elements, as Figure 4.12 shows:
group element. (Two important excep- For most main-group elements, the A-group number (1A, 2A, and so on)
tions are O, which never has an O.N. of
is the highest oxidation number (always positive) of any element in the
+6, and F, which never has an O.N. of
7.) For nonmetals (yellow) and metal- group. The exceptions are O and F (see Table 4.3).
loids (green), the A-group number For the main-group nonmetals and some metalloids, the A-group number
minus 8 gives the lowest possible minus 8 gives the lowest oxidation number (always negative) of any ele-
oxidation number. ment in the group.
4.3 Oxidation-Reduction (Redox) Reactions 151

For example, the highest oxidation number of S (Group 6A) is 6, as in SF6,

e
and the lowest is (6 8), or 2, as in FeS and other metal sulfides.
As you can see, the oxidation number for an element in a binary ionic
compound has a realistic value, because it usually equals the ionic charge. Transfer
X or shift of Y
On the other hand, the oxidation number has a very unrealistic value for an electrons
element in a covalent compound (or polyatomic ion) because whole charges
dont exist on the atoms in those species.
X loses Y gains
Another way to define a redox reaction is one in which the oxidation num- electron(s) electron(s)
bers of the species change, and the most important use of oxidation numbers is X is oxidized Y is reduced
to monitor these changes: X is the Y is the
If a given atom has a higher (more positive or less negative) oxidation reducing agent oxidizing agent
number in the product than it had in the reactant, the reactant molecule X increases in Y decreases in
or ion that contained the atom was oxidized (lost electrons). Thus, oxida- oxidation oxidation
number number
tion is represented by an increase in oxidation number.
If an atom has a lower (more negative or less positive) oxidation number
Figure 4.13 A summary of
in the product than it had in the reactant, the reactant molecule or ion terminology for oxidation-reduc-
that contained the atom was reduced (gained electrons). Thus, the gain of tion (redox) reactions.
electrons is represented by a decrease (a reduction) in oxidation number. (The
term reduction, as mentioned earlier, refers to an ore being reduced to
the metal. In modern terms, the reducing agents used, such as charcoal
and hydrogen, provide electrons that convert the metal ion to its elemen-
tal form.)
Figure 4.13 gives a compact summary of redox terminology. Since oxida-
tion numbers are assigned according to the atom that pulls more strongly on
the electrons, they are ultimately based on atomic properties, as youll see in
Chapters 8 and 9.

Sample Problem 4.7 Recognizing Oxidizing and Reducing Agents

PROBLEM Identify the oxidizing agent and reducing agent in each of the following:
(a) 2Al(s) 3H2SO4(aq) Al2(SO4)3(aq) 3H2(g)
(b) PbO(s) CO(g) Pb(s) CO2(g)
(c) 2H2(g) O2(g) 2H2O(g)
PLAN We first assign an oxidation number (O.N.) to each atom (or ion) based on
the rules in Table 4.3. The reactant is the reducing agent if it contains an atom that
is oxidized (O.N. increased in the reaction). The reactant is the oxidizing agent if it
contains an atom that is reduced (O.N. decreased).
SOLUTION (a) Assigning oxidation numbers:
6 6
0 1 2 3 2 0

2Al(s) 3H2SO4(aq) Al2(SO4)3(aq) 3H2(g)

The O.N. of Al increased from 0 to 3 (Al lost electrons), so Al was oxidized;
Al is the reducing agent.
The O.N. of H decreased from 1 to 0 (H gained electrons), so H was reduced;
H2SO4 is the oxidizing agent.
(b) Assigning oxidation numbers:
2 2 2
2 2 0 4

PbO(s) CO(g) Pb(s) CO2(g)

Pb decreased its O.N. from 2 to 0, so PbO was reduced; PbO is the oxidizing agent.
C increased its O.N. from 2 to 4, so CO was oxidized; CO is the reducing agent.
In general, when a substance (such as CO) bonds to more O atoms (as in CO2), it
is oxidized, and when a substance (such as PbO) bonds to fewer O atoms (as in
Pb), it is reduced.
152 Chapter 4 The Major Classes of Chemical Reactions

(c) Assigning oxidation numbers:

0 0 12

2H2(g) O2(g) 2H2O(g)

O2 was reduced (O.N. of O decreased from 0 to 2); O2 is the oxidizing agent.
H2 was oxidized (O.N. of H increased from 0 to 1); H2 is the reducing agent.
Oxygen is always the oxidizing agent in a combustion reaction.
COMMENT 1. Compare the O.N. values in (c) with those in another common reac-
tion that forms waterthe net ionic equation for an acid-base reaction:
1
1 2 12

H (aq) OH (aq) H2O(l)
Note that O.N. values remain the same on both sides of the acid-base equation.
Therefore, an acid-base reaction is not a redox reaction.
2. If an elemental substance occurs as reactant or product, it could not possibly be
in its elemental form on the other side of the equation, so the reaction must be a
redox process. Notice that elements appear in all three cases above.
Follow-up Problem 4.7 Identify the oxidizing agent and reducing agent in
the following:
(a) 2Fe(s) 3Cl2(g) 2FeCl3(s)
(b) 2C2H6(g) 7O2(g) 4CO2(g) 6H2O(g)
(c) 5CO(g) I2O5(s) I2(s) 5CO2(g)

Balancing Redox Equations

It is extremely important to realize that the reducing agent loses electrons and the
oxidizing agent gains them simultaneously. A chemical change cannot be an
oxidation reaction or a reduction reaction; only an oxidation-reduction
reaction can occur. The transferred electrons are never free, which means
that we can balance a redox reaction by making sure that the number of elec-
trons lost by the reducing agent equals the number of electrons gained by the oxidiz-
ing agent.
Two methods used to balance redox equations are the oxidation number
method and the half-reaction method. This section describes the oxidation
number method in detail; the half-reaction method is covered in Chapter 21.*
The oxidation number method for balancing redox equations consists
of five steps that use the changes in oxidation numbers to generate balanc-
ing coefficients. The first two steps are identical to those in Sample Problem
4.7:
Step 1. Assign oxidation numbers to all elements in the reaction.
Step 2. From the changes in oxidation numbers, identify the oxidized and
reduced species.
Step 3. Compute the number of electrons lost in the oxidation and gained in
the reduction from the oxidation number changes. (Draw tie-lines
between these atoms to show the changes.)
Step 4. Multiply one or both of these numbers by appropriate factors to make
the electrons lost equal the electrons gained, and use the factors as
balancing coefficients.
Step 5. Complete the balancing by inspection, adding states of matter.

*A thorough discussion of the half-reaction method appears in Section 21.1 for use in electro-
chemistry. However, if your professor chooses to cover that section here, it is completely trans-
ferrable with no loss in continuity.
4.3 Oxidation-Reduction (Redox) Reactions 153

Sample Problem 4.8 Balancing Redox Equations by the Oxidation

Number Method
PROBLEM Use the oxidation number method to balance the following equations:
(a) Cu(s) HNO3(aq) Cu(NO3)2(aq) NO2(g) H2O(l)
(b) PbS(s) O2(g) PbO(s) SO2(g)
SOLUTION (a) Step 1. Assign oxidation numbers to all elements:
5 5 2
0 1 2 2 2 4 12

Cu HNO3 Cu(NO3)2 NO2 H2O

Step 2. Identify oxidized and reduced species. The O.N. of Cu increased from 0 (in
Cu metal) to 2 (in Cu2); Cu was oxidized. The O.N. of N decreased from 5
(in HNO3) to 4 (in NO2); HNO3 was reduced. Note that some NO3 also acts as a
spectator ion, appearing unchanged in the Cu(NO3)2; this is quite common in redox
Copper in nitric acid.
reactions. We focus now on HNO3, the species in which N did change its O.N.
Step 3. Compute e lost and e gained and draw tie-lines between the atoms. In
the oxidation, 2e were lost from each Cu. In the reduction, 1e was gained by
each N:
2e

Cu HNO3 Cu(NO3)2 NO2 H2O

1e
Step 4. Multiply by factors to make e lost equal e gained, and use the factors as
coefficients. Cu lost 2e, so the 1e gained by N should be multiplied by 2. Using 2
as a coefficient for NO2 and HNO3 gives
Cu 2HNO3 Cu(NO3)2 2NO2 H2O
Step 5. Complete the balancing by inspection. Balancing N atoms requires a 4 in
front of HNO3 because of the additional two NO3 ions in Cu(NO3)2:
Cu 4HNO3 Cu(NO3)2 2NO2 H2O
Balancing H atoms requires a 2 in front of H2O, and we add states of matter:
Cu(s) 4HNO3(aq) Cu(NO3)2(aq) 2NO2(g) 2H2O(l)
CHECK Reactants (1 Cu, 4 H, 4 N, 12 O) products [1 Cu, 4 H, (2 2) N,
(6 4 2) O]
(b) Step 1. Assign oxidation numbers:
2 2 2
2 0 2 4

PbS O2 PbO SO2

Step 2. Identify species that are oxidized and reduced. PbS was oxidized. The O.N.
of S increased from 2 in PbS to 4 in SO2. O2 was reduced. The O.N. of O
decreased from 0 in O2 to 2 in PbO and in SO2.
Step 3. Compute e lost and e gained and draw tie-lines. The S lost 6e and each
O gained 2e:
6e

PbS O2 PbO SO2

4e (2e per O)

Step 4. Multiply by factors to make e lost equal e gained. The single S atom loses
6e. Each O in O2 gains 2e, for a total of 4e gained. Thus, using 32 as a coeffi-
cient of O2 gives 3 O atoms that each gain 2e, for a total of 6e gained:
PbS 32O2 PbO SO2
Step 5. Complete the balancing by inspection. The atoms are balanced, but all coeffi-
cients must be multiplied by 2 to obtain integers, and we add states of matter:
2PbS(s) 3O2(g) 2PbO(s) 2SO2(g)
154 Chapter 4 The Major Classes of Chemical Reactions

CHECK Reactants (2 Pb, 2 S, 6 O) products [2 Pb, 2 S, (2 4) O]

Follow-up Problem 4.8 Use the oxidation number method to balance the
following: K2Cr2O7(aq) HI(aq) KI(aq) CrI3(aq) I2(s) H2O(l)

Redox Titrations
Just as a base is used to find the concentration of an acid (or vice versa) in
an acid-base titration, a known concentration of an oxidizing agent can be
used to find the unknown concentration of a reducing agent (or vice versa)
in a redox titration. This application of stoichiometry is used in a wide range
of situations, including measuring the iron content in drinking water and the
vitamin C content in fruits and vegetables.
The permanganate ion, MnO4, is a common oxidizing agent in these titra-
tions because it is strongly colored and, thus, also serves as an indicator. In
the following example, MnO4 oxidizes the oxalate ion, C2O42 to determine
its concentration. As long as any C2O42 is present, it reduces the deep pur-
ple MnO4 to the very faint pink (nearly colorless) Mn2 ion (Figure 4.14,
left). As soon as all the available C2O42 has been oxidized, the next drop of
MnO4 turns the solution light purple (Figure 4.14, right). This color change
indicates the end point, the point at which the electrons lost by the oxidized
species (C2O42) equal the electrons gained by the reduced species (MnO4).
We then calculate the concentration of the C2O42 solution from its known
volume, the known volume and concentration of the MnO4 solution, and
the balanced equation.
Preparing a sample for a redox titration sometimes requires several labo-
ratory steps. In Sample Problem 4.9, for instance, the Ca2 ion concentration
of blood is determined. The Ca2 is first precipitated as calcium oxalate
(CaC2O4). Dilute H2SO4 dissolves the precipitate and releases the C2O42 ion,
which is then titrated with standardized MnO4 ion. After the C2O42 con-
centration has been determined, it is used to find the original blood Ca2
concentration.

Net ionic equation:

+7 +3 +2 +4
2MnO4(aq ) + 5C2O42(aq ) + 16H+(aq ) 2Mn2+(aq ) + 10CO2(g) + 8H2O(l )

Figure 4.14 A redox titration. The oxidizing agent in the buret, KMnO4, is strongly colored,
so it also serves as the indicator. When it reacts with the reducing agent C2O42 in the flask, its
color changes from deep purple to almost colorless (left). When all the C2O42 is oxidized, the
next drop of KMnO4 remains unreacted and turns the solution light purple (right), signaling the
end point of the titration.
4.3 Oxidation-Reduction (Redox) Reactions 155

Sample Problem 4.9 Finding an Unknown Concentration by a

Redox Titration
PROBLEM Calcium ion (Ca2) is required for blood to clot and for many other
biological processes. An abnormal Ca2 concentration is indicative of several dis-
eases. To measure the Ca2 concentration, 1.00 mL of human blood was treated
with Na2C2O4 solution. The resulting CaC2O4 precipitate was dissolved in dilute
H2SO4. This solution required 2.05 mL of 4.88104 M KMnO4 to reach the titra-
tion end point.
(a) Calculate the amount (mol) of Ca2.
(b) Calculate the Ca2 ion concentration expressed in units of mg Ca2/100 mL
blood.
(a) Calculating the moles of Ca2
PLAN As always, we first write the balanced equation. All the Ca2 ion in the Volume (L) of KMnO4 solution
blood sample is precipitated and then dissolved in the H2SO4. We find the number
of moles of KMnO4 needed to reach the end point and use the molar ratio to cal- multiply by
culate the number of moles of CaC2O4 dissolved in the H2SO4. Then, from the M (mol/L)
chemical formula, we find moles of Ca2 ions.
SOLUTION Writing the balanced equation: Amount (mol) of KMnO4
2KMnO4(aq) 5CaC2O4(aq) 8H2SO4(aq)
2MnSO4(aq) K2SO4(aq) 5CaSO4(aq) 10CO2(g) 8H2O(l) molar ratio

Converting from volume (mL) to moles of KMnO4 used to reach the end point:
1L 4.88104 mol KMnO4
Moles of KMnO4 2.05 mL soln Amount (mol) of CaC2O4
1000 mL 1 L soln
1.00106 mol KMnO4 ratio of elements in
Converting from moles of KMnO4 to moles of CaC2O4 titrated: chemical formula

5 mol CaC2O4
Moles of CaC2O4 1.00106 mol KMnO4 Amount (mol) of Ca2+
2 mol KMnO4
2.50106 mol CaC2O4
Finding moles of Ca2 present:
1 mol Ca2
Moles of Ca2 2.50106 mol CaC2O4
1 mol CaC2O4
2.50106 mol Ca2
CHECK A very small volume of dilute KMnO4 is needed, so 106 mol of KMnO4
seems reasonable. The molar ratio of 5CaC2O4/2KMnO4 gives 2.5106 mol of
CaC2O4 and thus 2.5106 mol of Ca2.
(b) Expressing the Ca2 concentration as mg/100 mL blood
PLAN The amount in part (a) is the moles of Ca2 ion present in 1.00 mL blood. Amount (mol) of Ca2+/1 mL blood
We multiply by 100 to obtain the moles of Ca2 ion in 100 mL blood, and then
convert to milligrams of Ca2/100 mL blood. multiply by 100
SOLUTION Finding moles of Ca2/100 mL blood:
2.50106 mol Ca2
Moles of Ca2100 mL blood 100 Amount (mol) of Ca2+/100 mL blood
1.00 mL blood
2.50104 mol Ca2100 mL blood
multiply by
Converting from moles of Ca2 to milligrams: (g/mol)
2.50104 mol Ca2 40.08 g Ca2 1000 mg
Mass (mg) Ca2100 mL blood 2

100 mL blood 1 mol Ca 1g Mass (g) of Ca2+/100 mL blood

10.0 mg Ca2100 mL blood

1 g = 1000 mg
CHECK The relative amounts of Ca2 make sense. If there is 2.5106 mol/mL
blood, there is 2.5104 mol/100 mL blood. A molar mass of about 40 g/mol for
Ca2 gives 100104 g, or 10103 g/100 mL blood. It is easy to make an order-
of-magnitude (power of 10) error in this type of calculation, so be sure to include Mass (mg) of Ca2+/100 mL blood
all units.
156 Chapter 4 The Major Classes of Chemical Reactions

COMMENT 1. The normal range of Ca2 concentration in a human adult is 9.0 to

11.5 mg Ca2/100 mL blood, so our value seems reasonable.
2. When blood is donated, the receiving bag contains Na2C2O4 solution, which
precipitates the Ca2 ion and, thus, prevents clotting.
3. A redox titration is analogous to an acid-base titration: in redox processes, elec-
trons are lost and gained, whereas in acid-base processes, H ions are lost and
gained.
Follow-up Problem 4.9 A 2.50-mL sample of low-fat milk was treated with
sodium oxalate, and the precipitate was dissolved in H2SO4. This solution required
6.53 mL of 4.56103 M KMnO4 to reach the end point.
(a) Calculate the molarity of Ca2 in the milk.
(b) What is the concentration of Ca2 in g/L? Is this value consistent with the
typical value in milk of about 1.2 g Ca2/L?

Section Summary
When there is a net movement of electron charge from one reactant to
another, a redox process takes place. Electron gain (reduction) and electron
loss (oxidation) occur simultaneously. The redox process is tracked by assign-
ing oxidation numbers to each atom in a reaction. The species that is oxi-
dized (contains an atom that increases in oxidation number) is the reducing
agent; the species that is reduced (contains an atom that decreases in oxida-
tion number) is the oxidizing agent. Redox reactions can be balanced by
keeping track of the changes in oxidation number. A redox titration is used
to determine the concentration of either the oxidizing or the reducing agent
from the known concentration of the other.

4.4 Counting Reactants and Products in

Precipitation, Acid-Base, and Redox Processes
In previous sections, we classified chemical change according to one of the
three major reaction processesprecipitation, acid-base, or oxidation-reduc-
tion. In this section, we overlap that classification scheme with a more his-
torical one that relies on counting the numbers of reactants and products.
One key point is that whenever an element is involved as either reactant or prod-
uct, the change is a redox reaction. In fact, as youll see, redox reactions domi-
nate the reaction classes shown.
By definition, the essence of any reaction is that atoms or ions change
their chemical attachments. Elements combine into compounds, or com-
pounds decompose into elements. Large molecules break apart, or small mol-
ecules join together. In some cases, the atoms (or ions) in two compounds
switch bonding partners to form a new pair of compounds. When we com-
pare the number of reactant and product substances, three broad types of
reactions arisecombination, decomposition, and displacement. We also con-
sider a fourth type, combustion reactions, which have been used for millen-
nia and understood ever since Lavoisiers experiments over two centuries ago.

Combination Reactions
In combination reactions, two or more reactants combine to form one product:
X Y Z. The following discussion organizes combination reactions by
kinds of reactants.
4.4 Counting Reactants and Products in Precipitation, Acid-Base, and Redox Processes 157

K+ Cl
K K+ Cl
K

Cl2

0 0 +1 -1
2K(s) + Cl2( g ) 2KCl(s)
Potassium Chlorine Potassium chloride

Figure 4.15 Three views of a combination reaction be- laboratory. The blow-up arrows lead to an atomic-scale view (mid-
tween elements. When the metal potassium and the nonmetal dle); the stoichiometry is indicated by the more darkly colored
chlorine react, they form the solid ionic compound potassium chlo- spheres. The balanced redox equation is shown with oxidation
ride. The photos (top) present the view the chemist sees in the numbers (bottom).

Combination Reactions That Are Redox Reactions Note that in all the
examples shown, an element appears as a reactant.
1. Combination of two elements. Two elements react to form binary ionic or
covalent compounds. In every case, there is a net change in the distribution
of electron charge, which means the elements change their oxidation num-
bers. Here are some important examples:
A metal and a nonmetal form an ionic compound. Figure 4.15 shows the reac-
tion between an alkali metal and a halogen on three levelsobservable,
atomic, and symbolic. Note the change in oxidation numbers. Thus, K is
the reducing agent and Cl2 is the oxidizing agent. Metals react with O2 to
form ionic oxides:
0 0 3 2

2Al(s) 3O2(g) Al2O3(s)

158 Chapter 4 The Major Classes of Chemical Reactions

Two nonmetals form a covalent compound. In one of thousands of examples,

ammonia forms from nitrogen and hydrogen in a reaction that occurs in
industry on an enormous scale:
1
0 0 3

N2(g) 3H2(g) 2NH3(g)

Halogens form many compounds with other nonmetals, as in the forma-
tion of phosphorus trichloride, a major reactant in the production of pes-
ticides and other organic compounds:
1
0 0 3

P4(s) 6Cl2(g) 4PCl3(l)

Nearly every nonmetal reacts with O2 to form a covalent oxide, as when
nitrogen monoxide forms at the very high temperatures created in air by
lightning:
2
0 0 2

N2(g) O2(g) 2NO(g)

2. Combination of a compound and an element. Many binary covalent com-
pounds react with nonmetals to form larger compounds. Many nonmetal
oxides react with additional O2 to form higher oxides (those with more O
atoms in each molecule). For example, a key step in the generation of urban
smog is
2 2
2 0 4

2NO(g) O2(g) 2NO2(g)

Similarly, many nonmetal halides combine with additional halogen:
1 1
3 0 5

PCl3(l) Cl2(g) PCl5(s)

Combination Reactions That Are Not Redox Reactions Most combination

reactions that involve only compounds as reactants are not oxidation-reduction reac-
tions. (A few are redox reactions, however, so always check oxidation num-
bers to be sure.)
1. A metal oxide and a nonmetal oxide form an ionic compound with a polyatomic
anion. One example is the formation of a metal carbonate, such as the drug
lithium carbonate, from the metal oxide and carbon dioxide; note that the
oxidation numbers do not change:
2 4
12 4 1 2

Li2O(s) CO2(g) Li2CO3(s)

The pattern in this and other such reactions is that the O2 ion in the metal
oxide combines with the nonmetal oxide to form the polyatomic oxoanion.
2. Metal oxides and water form bases. Lime (calcium oxide) added to soil can
provide a proper acid-base balance by forming slaked lime (calcium hydrox-
ide):
CaO(s) H2O(l) Ca(OH)2(aq)
3. Nonmetal oxides and water form acids. Sulfur trioxide and water form sul-
furic acid, the most abundantly produced chemical in the world:
SO3(g) H2O(l) H2SO4(aq)
4.4 Counting Reactants and Products in Precipitation, Acid-Base, and Redox Processes 159

Decomposition Reactions
Decomposition reactions are the reverse of combination reactions: one
reactant breaks down into two or more products, Z X Y. They occur
when the reactant absorbs enough energy for one or more of its bonds to
break. Like a combination reaction, a decomposition reaction is a redox process if
an element is involved in the change. In the combination the element is a reac-
tant; in the decomposition it is a product.
Thermal Decomposition When the energy absorbed is heat, the reaction is
a thermal decomposition. A delta, , above a yield arrow indicates that heat
is required for the reaction.
1. Many ionic compounds with oxoanions form a metal oxide and a gaseous non-
metal oxide. Carbonates yield CO2 when heated (and sulfites yield SO2). More
than 200 million tons of lime are produced annually for cement, glass, and
steel manufacture by heating limestone (calcium carbonate):
CaCO3(s) CaO(s) CO2(g)
2. Many metal oxides, chlorates, and perchlorates release oxygen. Since an ele-
ment is formed, these are redox reactions. The decomposition of mercury(II)
oxide, used by Lavoisier and Priestley in their classic experiments, is an
example. Figure 4.16 shows three representations of the reaction.

O 2 Hg
O 2
Hg2+ Hg2+ Hg

O2

+2 -2 0 0
2HgO(s) 2Hg(l ) + O2( g )
Mercury(II) oxide Mercury Oxygen

Figure 4.16 Three views of a decomposition reaction that (laboratory) view (top); the atomic-scale view, with the more darkly
forms elements. Heating solid mercury(II) oxide decomposes it to colored spheres showing the stoichiometry (middle); and the bal-
its elements, liquid mercury and gaseous oxygen: the macroscopic anced redox equation (bottom).
160 Chapter 4 The Major Classes of Chemical Reactions

Heating potassium chlorate is a modern method for forming small amounts

of oxygen in the laboratory:
5 1
1 2 1 0

2KClO3(s) 2KCl(s) 3O2(g)
Notice that, in these cases, the lone reactant is the oxidizing and the reduc-
ing agent. For example, in HgO, O2 reduces Hg2 (and Hg2 oxidizes O2).

Electrolytic Decomposition Many compounds that absorb electrical energy

decompose into their elements by the process of electrolysis. Such processes
are redox reactions.
1. Decomposition of water. This reaction (see Figure 1.1B) was a key obser-
vation in the establishment of atomic masses:
12 0 0
electricity
2H2O(l) 2H2(g) O2(g)
2. Decomposition of molten ionic compounds. Sodium, magnesium, calcium, and
several other metals are produced industrially by electrolysis of their molten
halides:
2 1 0 0
electricity
MgCl2(l) Mg(l) Cl2(g)

Displacement Reactions
Metathesis and Plastic Displacement (or replacement) reactions have the same number of reactants
Bags Although metathesis as products. They occur when an atom (or ion) in a compound is displaced
(double-displacement) reactions in by a different atom (or ion). Displacement reactions are either single-dis-
aqueous solution are our focus in
placement or double-displacement (metathesis; pronounced meh-TATH-uh-
this discussion, these reactions can
sis) reactions:
occur in organic solvents as well.
This reaction type is currently being X YZ XZ Y [single]
applied by polymer chemists as a WX YZ WZ YX [double; metathesis]
new way to prepare poly(ethylene),
Even though both types involve displacement, they differ fundamentally in
the material used in plastic
shopping bags. At the same time, the chemical nature of the underlying process:
metathesis reactions are being Single-displacement reactions are oxidation-reduction reactions.
studied as a means of controlled Metathesis reactions include precipitation and acid-base reactions.
disassembling of long polymer
chains for plastic recycling. Single-Displacement Reactions; The Activity Series of the Metals Metals
vary in their reactivity. They can be ranked according to their ability to dis-
place H2 from various sources or to displace one another from solution. Some
nonmetals, especially the halogens, vary in their reactivity as well, and the
differences can be seen in their ability to displace one another from solution.
1. A metal displaces H2 from water or acid. The most reactive metals, such as
those from Group 1A(1) and Ca, Sr, and Ba from Group 2A(2), displace H2
from water, and they do so vigorously. Figure 4.17 shows the laboratory view,
the atomic view, and the balanced equation of this reaction for lithium. Heat
is needed to speed the reaction of less reactive metals, such as aluminum and
zinc, so these displace H2 from steam:
1
0 12 3 2 0

2Al(s) 6H2O(g) 2Al(OH)3(s) 3H2(g)

4.4 Counting Reactants and Products in Precipitation, Acid-Base, and Redox Processes 161

H2O
OH

Li Li Li+

Li+

H2
OH
H2O

0 +1 -2 +1 -2 +1 0
2Li(s) + 2H2O(l ) 2LiOH(aq ) + H2 ( g )
Lithium Water Lithium hydroxide Hydrogen

Figure 4.17 Three views of a single-displacement reac- dle), and as a balanced equation (bottom). (For clarity, the atomic
tion. Lithium displaces hydrogen from water in a vigorous reaction view of water has been greatly simplified, and only water molecules
that yields an aqueous solution of lithium hydroxide and hydrogen involved in the reaction are colored red and blue.)
gas, as shown on the macroscopic scale (top), atomic scale (mid-

Still less reactive metals, such as nickel and tin, do not react with water but
do react with acids, from which H2 is displaced more easily (Figure 4.18).
Here is the net ionic equation:
0 1 2 0

Ni(s) 2H (aq) Ni (aq) H2(g)
2

Notice that in all such reactions, the metal is the reducing agent (O.N. of
metal increases) and water or acid is the oxidizing agent (O.N. of H
decreases). The least reactive metals, such as silver and gold, cannot displace
H2 from any source.
2. A metal displaces another metal ion from solution. Direct comparisons of
metal reactivity are clearest in these reactions. For example, zinc metal dis-
places copper(II) ion from solution, as the net ionic equation shows: Figure 4.18 The displacement of
2 0 0 2 H2 from acid by nickel.

Cu2(aq) Zn(s) Cu(s) Zn2(aq)

162 Chapter 4 The Major Classes of Chemical Reactions

Figure 4.19 Three views of cop-

per displacing silver ions from
solution. More reactive metals can
displace less reactive ones from solu-
tion. In this single-displacement reac-
tion, Cu atoms become Cu2 ions and
leave the wire, as they transfer electrons
to two Ag ions that become Ag atoms Copper wire
and coat the wire: the laboratory view Copper coated with
(top), the atomic view (middle), and the wire silver
balanced redox equation (bottom). Copper
Silver nitrate
nitrate solution
solution

Ag +
2e Cu 2+

Ag +

Ag atoms
coating
wire Cu atoms
in wire

+1 +5 -2 0 +2 +5 -2 0
2AgNO3(aq) + Cu(s) Cu(NO3)2(aq) + 2Ag(s)

Li
Displace H2
from water

K
Ba Figure 4.19 shows in atomic detail that Cu metal can, in turn, displace Ag
Ca ion from solution. Thus, Zn is more reactive than Cu, which is more reac-
Displace H2

Na
from steam

tive than Ag.

Mg
Strength as reducing agent

The results of many such single-displacement reactions between metals

Displace H2

Al
and water, aqueous acids, and metal-ion solutions form the basis of the activ-
from acid

Mn
ity series of the metals. It is shown in Figure 4.20 as a list arranged in
Zn
Cr
order of decreasing strength of the metal as a reducing agent. Thus, elements higher
Fe on the list are stronger reducing agents than elements lower down. In other
Cd words, for those elements stable in water, elements higher on the list can dis-
Co place from aqueous solution the ions of elements lower down. The list also
Ni shows whether the metal can displace H2 and, if so, from which source. Using
Sn just the examples weve already discussed, you can see that Li, Al, and Ni lie
Pb above H2, whereas Ag lies below it, and that Zn lies above Cu, which lies
H2 above Ag.
Cu
displace H2

3. A halogen displaces a halide ion from solution. Reactivity decreases down

Do not

Hg
Group 7A(17). Therefore, a halogen higher in the group can displace one
Ag
lower down from aqueous solution. In this reaction, chlorine displaces
Au
bromine:
1 0 0 1
Figure 4.20 The activity series
of the metals. This list of metals (and 2Br (aq) Cl2(aq) Br2(aq) 2Cl(aq)

H2) is arranged with the most active

metal (strongest reducing agent) at the Double-Displacement Reactions Precipitation and acid-base reactions are
top and the least active (weakest re- the most important examples of metathesis reactions (see Section 4.2). Be-
ducing agent) at the bottom. The four
metals below H2 cannot displace it
cause none of the atoms changes its oxidation number, these are not redox
from any source. (The ranking refers processes. The following reactions are written as molecular equations with
to behavior in aqueous solution.) colored atoms to emphasize their double-displacement aspect.
4.4 Counting Reactants and Products in Precipitation, Acid-Base, and Redox Processes 163

1. In precipitation reactions, an insoluble ionic compound forms. Silver bromide, Amino acid units
which is used to manufacture black-and-white film, forms in a double-dis-
placement reaction:
AgNO3(aq) KBr(aq) AgBr(s) KNO3(aq) Protein
molecule
2. In acid-base reactions, an acid and a base form a salt and water. Aluminum
H2 O
hydroxide, the active ingredient in some antacid tablets, acts by a double- H2O
displacement reaction:
3HCl(aq) Al(OH)3(s) AlCl3(aq) 3H2O(l)
Displacement reactions occur frequently in the synthesis and breakdown of Synthesis of Breakdown of
organisms food proteins
biological macromolecules. proteins

Combustion Reactions Combustion is the process of combining with oxy-

gen, usually with the release of large amounts of heat and light, often as a
flame. Burning in air is a common example. Since O2 is a reactant, all
combustion reactions are redox processes.
These very common and essential reactions do not always fall neatly into
classes based on the number of reactants and products, but the combustion Amino acid molecules

of an element, such as the burning of sulfur, is always a combination reaction Displacement Reactions
because two substances form one: Inside You The digestion of
S8(s) 8O2(g) 8SO2(g) food proteins is joined to the for-
mation of a cells own proteins in
The combustion reactions we use to produce energy involve organic mix- continuous cycles of displacement
tures such as coal, gasoline, or natural gas as reactants. These mixtures con- reactions. A protein consists of
sist of substances with many carbon-carbon and carbon-hydrogen bonds. hundreds or thousands of smaller
During the reaction, these bonds break, and each C and H atom combines molecules, called amino acids, linked
with oxygen. Therefore, the products typically consist of CO2 and H2O. The in a long chain. When you eat
combustion of the hydrocarbon butane, which is used in cigarette lighters, is proteins, your digestive processes
typical: use H2O to displace one amino acid
at a time. These are transported by
2C4H10(g) 13O2(g) 8CO2(g) 10H2O(g) the blood to your cells, where other
Cellular respiration can be thought of as a combustion process that occurs metabolic processes link them
within our bodies cellsfortunately without flamewhen we burn together, displacing H2O, to make
organic foodstuffs, such as glucose, for energy: your own proteins.
C6H12O6(s) 6O2(g) 6CO2(g) 6H2O(g) energy

Sample Problem 4.10 Identifying the Type of Chemical Reaction Space-Age Combustion
PROBLEM Classify the following as combination, decomposition, or displacement Without a Flame
reactions, identify the underlying chemical process as precipitation, acid-base, or Combustion reactions are used to
redox, and write a balanced molecular equation for each. For any that are redox, generate large amounts of energy.
identify the oxidizing and reducing agents: In most common applications, the
(a) Lead(II) acetate(aq) sodium sulfate(aq) fuel is burned and the energy is
lead(II) sulfate(s) sodium acetate(aq) released as heat (in a furnace) or as
(b) Magnesium(s) nitrogen(g) magnesium nitride(s) a combination of work and heat (in
(c) CH2(COOH)2(s) sodium hydroxide(aq) CH2(COONa)2(aq) water a combustion engine). Aboard the
(d) Hydrogen peroxide(l) water oxygen gas Space Shuttle, devices called fuel
(e) Aluminum(s) lead(II) nitrate(aq) aluminum nitrate(aq) lead(s) cells generate electrical energy from
PLAN To decide on reaction type, we recall that combination reactions produce the flameless combustion of hydro-
fewer substances, decomposition reactions more substances, and displacement reac- gen gas. The H2 is the reducing
tions the same number of substances. For precipitation processes, a solid forms; for agent, and O2 is the oxidizing agent
acid-base, water and a salt form; and for redox, oxidation numbers change. The in a complex, controlled reaction
O.N. becomes more positive for the reducing agent and less positive for the oxidiz- process that yields waterwhich
ing agent. the astronauts use for drinking.
SOLUTION (a) Displacement (metathesis): two substances form two. This On Earth, fuel cells based on the
precipitation reaction forms a common white pigment: reaction of methanol (CH3OH) and
O2 are being investigated for use in
Pb(C2H3O2)2(aq) Na2SO4(aq) PbSO4(s) 2NaC2H3O2(aq) automobile engines.
164 Chapter 4 The Major Classes of Chemical Reactions

(b) Combination: two substances form one. This redox reaction occurs, along
with formation of the metal oxide, when magnesium burns in air:
0 0 2 3

3Mg(s) N2(g) Mg3N2(s)

Mg is the reducing agent; N2 is the oxidizing agent.
(c) Displacement (metathesis): two substances form two. The biomolecule malonic
acid reacts with sodium hydroxide in this acid-base reaction. The two H ions
from the acid (COOH) groups are transferred to the hydroxide ions to form
water:
CH2(COOH)2(s) 2NaOH(aq) CH2(COONa)2(aq) 2H2O(l)
(d) Decomposition: one substance forms two. This redox reaction occurs within
every bottle of this common household antiseptic. Hydrogen peroxide is very un-
stable and breaks down easily by heat, light, or just shaking:
11 12 0

2H2O2(l) 2H2O(l) O2(g)

H2O2 is both oxidizing and reducing agent. (Note that the O.N. of O in peroxides
is 1.)
(e) Displacement (single): two substances form two. This redox reaction occurs
when the more reactive Al displaces the less reactive Pb (see Figure 4.20):
2 2
0 2 5 3 5 0

2Al(s) 3Pb(NO3)2(aq) 2Al(NO3)3(aq) 3Pb(s)

Al is the reducing agent; Pb(NO3)2 is the oxidizing agent.
Follow-up Problem 4.10 Classify each of the following reactions by number
of reactants and products and by underlying chemical process, and write a balanced
equation. Identify the oxidizing and reducing agents in any redox reactions:
(a) S8(s) F2(g) SF4(g)
(b) Na2SO3(aq) HCl(aq) NaCl(aq) SO2(g) H2O(l)
(c) Ni(NO3)2(aq) Cr(s) Cr(NO3)3(aq) Ni(s)

Section Summary
Any reaction with a substance in its elemental form as reactant or product
is a redox reaction. Another way to classify reactions is by counting numbers
of reactants and products. Combination reactions occur when two or more
substances form one. All reactions between elements are of this type. In
decomposition reactions, one substance forms two or more, usually by
absorbing heat or electrical energy. In displacement reactions, the numbers
of reactants and products are equal. Single-displacement reactions can rank
metal (or halogen) reactivity by the ability to displace H2 from water or acid
or one another from solution. Precipitation and acid-base processes are com-
mon types of double-displacement (metathesis) reactions. Combustion reac-
tions release energy through combination of a substance with O2.

4.5 Reversible Reactions: An Introduction to

Chemical Equilibrium
So far, we have viewed reactions as occurring from left to right, from reac-
tants to products and continuing until they are complete, that is, until the
limiting reactant is used up. However, many reactions seem to stop before
this happens. The reason is that another reaction, the reverse of the first one,
is also taking place. The forward (left-to-right) reaction has not stopped, but
the reverse (right-to-left) reaction is taking place at the same rate. Therefore,
4.5 Reversible Reactions: An Introduction to Chemical Equilibrium 165

no further changes occur in the amounts of reactants or products. At this point, the
reaction mixture has reached dynamic equilibrium. On the macroscopic
scale, the reaction is static, but it is dynamic on the molecular scale. In prin-
ciple, all reactions are reversible and will eventually reach dynamic equilib-
rium as long as all products remain available for the reverse reaction.
Lets examine equilibrium with a particular set of substances. Calcium car-
bonate can decompose to calcium oxide and carbon dioxide:
CaCO3(s) CaO(s) CO2(g) [decomposition]
It can also form when calcium oxide and carbon dioxide combine:
CaO(s) CO2(g) CaCO3(s) [combination]
The combination is just the reverse of the decomposi-
tion. Suppose we place 10 g CaCO3 in an open steel reac-
tion flask and heat it to around 900C, as shown in Fig-
ure 4.21A. The CaCO3 starts decomposing to CaO and Decomposition CO2
CO2, and the CO2 escapes from the open flask. The CaCO3
goes to forms and
is heated
decomposition goes to completion because the reverse completion escapes CaO
reaction (combination) can occur only if CO2 is present.
In Figure 4.21B, we perform the same experiment in
a closed steel flask, so that the CO2 remains in contact CaCO3(s) CaO(s) + CO2(g)
with the CaO. The decomposition (forward reaction) A Nonequilibrium system
begins, but at first, when very little CaCO3 has decom-
posed, very little CO2 and CaO are available to combine,
so the combination (reverse reaction) just barely begins.
As the CaCO3 continues to decompose, the concentra-
tions of CO2 and CaO in the flask increase. The CO2 and
CaO react with each other more frequently, and the
combination occurs a bit faster. As the CaO and CO2
concentrations increase, the combination reaction grad- Decomposition Mixture of
CaCO3 CO2
ually speeds up. Eventually, the reverse reaction (com- and combination CaO and CaCO3
is heated forms
reach equilibrium
bination) happens just as fast as the forward reaction
(decomposition), and the amounts of CaCO3, CaO, and
CO2 no longer change: the system has reached equilib-
rium. We indicate a reaction at equilibrium with a pair CaCO3(s) CaCO3(s) CaO(s) + CO2(g)

of arrows pointing in opposite directions: B Equilibrium system

CaCO3(s) A CaO(s) CO2(g)
B Figure 4.21 The equilibrium
state. A, In an open steel reaction
Bear in mind that equilibrium can be established only when all the substances chamber, strong heating of CaCO3
involved are kept in contact with each other. The decomposition of CaCO3 goes to decomposes it completely because the
completion in the open flask because the CO2 escapes. product CO2 escapes and is not present
Aqueous acid-base reactions that form a gaseous product go to completion to react with the other product, CaO.
in an open flask for the same reason: the gas escapes, so the reverse reac- B, When CaCO3 decomposes in a
closed chamber, the CO2 is present to
tion cannot take place. Precipitation and other acid-base reactions also go to combine with CaO and re-form CaCO3
completion, even though all the products remain in the reaction vessel. In in a reaction that is the reverse of the
those cases, the ions are unavailable for the reverse process to occur, because decomposition. At a given temperature,
they are tied up either as an insoluble solid (precipitation) or as water mol- no further change in the amounts of
ecules (acid-base). products and reactants means that the
reaction has reached equilibrium.
The concept of reaction reversibility also explains why some acids and
bases are weak electrolytes, that is, why they dissociate into ions only to a
small extent. The dissociation quickly becomes balanced by a reassociation,
such that equilibrium is reached with very few ions present. For example,
when acetic acid dissolves in water, some of the CH3COOH molecules trans-
fer a proton to H2O and form H3O and CH3COO ions. As more ions form,
they react with each other more often to re-form acetic acid and water:
CH3COOH(aq) H2O(l) B
A H3O(aq) CH3COO(aq)
166 Chapter 4 The Major Classes of Chemical Reactions

In fact, in 0.1 M CH3COOH at 25C, only about 1.3% of the acid molecules
are dissociated at any given moment. Similarly, the weak base ammonia
reacts with water to form ions. As the product ions interact, the rate of the
reverse reaction soon balances the forward one:
NH3(aq) H2O(l) B
A NH4(aq) OH(aq)
Dynamic equilibrium is fundamental to the functioning of many natural
systems, from the cycling of water in the environment to the population bal-
ance of lion and antelope on the plains of Africa to the nuclear processes
occurring in stars. We return to the applications of equilibrium in chemical
and physical systems in Chapters 12, 13, and 17 through 21.

Section Summary
Every reaction is reversible if all the substances are kept in contact with one
another. As the amounts of products increase, the reactants begin to re-form.
When the reverse reaction happens as rapidly as the forward reaction, the
amounts of the substances no longer change, and the reaction mixture has
reached dynamic equilibrium. A reaction goes to completion if products are
removed from the system (as a gas) or exist in a form that prevents them
from reacting (precipitate or undissociated molecule). Weak acids and bases
reach equilibrium in water with a very small proportion of their molecules
dissociated.

Chapter Perspective
Classifying facts is the first step toward understanding them, the central question of why physical and chemical changes oc-
and this chapter has classified many of the most important cur. All these topics appear again at many places in the text.
facts of reaction chemistry into three major processesprecip- In the next chapter, our focus changes to the physical be-
itation, acid-base, and oxidation-reduction. We also examined havior of gases. Youll find that your growing appreciation of
the great influence that water has on reaction chemistry and events on the molecular level has become indispensable for un-
introduced the dynamic equilibrium state, which is related to derstanding the nature of the three physical states.
The following learning objectives, with section and/or sample problem (SP) numbers in parentheses, can help
focus your study:
Understand These Concepts 7. The essential character of aqueous acid-base reac-
1. How water dissolves ionic compounds and dissoci- tions as proton-transfer processes (4.2)
ates them into ions (4.1) 8. The importance of net movement of electrons in
2. Distinguish between the species present when the redox process (4.3)
ionic and covalent compounds dissolve in water; 9. The relation between change in oxidation number
distinguish between strong and weak electrolytes and identity of oxidizing and reducing agents (4.3)
(4.1) 10. The important types of redox reactions: combina-
3. The driving force for aqueous ionic reactions (4.2) tions involving elements, decomposition, single
4. The use of ionic equations to specify the essential displacement (4.4)
nature of an aqueous reaction (4.2) 11. The balance between forward and reverse rates of
5. How to decide whether a precipitation reaction a chemical reaction that leads to the equilibrium
occurs (4.2) state; why some acids and bases are weak (4.5)
6. The main distinction between strong and weak
aqueous acids and bases (4.2)
For Review and Reference 167

Master These Skills 6. Determining the oxidation number of any atom in

1. Using the formula of a compound to find the num- a compound (SP 4.6)
ber of moles of ions in solution (SP 4.1) 7. Selecting the oxidizing and reducing agents in a
2. Determining the concentration of H ion in an redox reaction (SP 4.7)
aqueous acid solution (SP 4.2) 8. Balancing redox equations (SP 4.8)
3. Predicting the formula of a precipitate (SP 4.3) 9. Determining the chemical nature of combination,
4. Writing ionic equations to describe precipitation decomposition, and displacement reactions
and acid-base reactions (SPs 4.3 and 4.4) (SP 4.10); predicting the products of a single
5. Calculating an unknown concentration from an displacement reaction
acid-base or redox titration (SPs 4.5 and 4.9)

For Review and Reference

Key Terms net ionic equation end point Section 4.4
precipitation Section 4.3 combination reaction
Section 4.1 precipitate oxidation-reduction decomposition reaction
electrolyte acid-base reaction (redox) reaction displacement reaction
solvated neutralization reaction oxidation metathesis reaction
polar molecule acid reduction activity series of the metals
nonelectrolyte base oxidizing agent Section 4.5
Section 4.2 salt reducing agent dynamic equilibrium
molecular equation titration oxidation number (O.N.)
total ionic equation acid-base indicator (or oxidation state)
spectator ion equivalence point oxidation number method

Highlighted Figures and Tables

These figures (F) and tables (T) provide a quick review of F4.9 An aqueous strong acidstrong base reaction on the
key ideas. Entries in color contain frequently used data. atomic scale (p. 146)
F4.2 Electron distribution in H2 and H2O (p. 136) F4.11 The redox process in compound formation (p. 149)
F4.3 Dissolution of an ionic compound (p. 137) T4.3 Rules for assigning an oxidation number (p. 150)
F4.6 Depicting a precipitation reaction with ionic equations F4.12 Highest and lowest oxidation numbers of reactive
(p. 140) main-group elements (p. 150)
T4.1 Solubility rules for ionic compounds (p. 141) F4.13 A summary of terminology for redox reactions (p. 151)
T4.2 Common acids and bases (p. 143) F4.20 The activity series of the metals (p. 162)

Answers to Follow-up Problems

4.3 (a) Fe3(aq) 3Cl(aq) 3Cs(aq) PO43(aq)
H O
4.1 (a) KClO4(s)
2
K(aq) ClO4(aq);

2 mol K and 2 mol ClO4 FePO4(s) 3Cl(aq) 3Cs(aq)
H2O
(b) Mg(C2H3O2)2(s) Mg2(aq) 2C2H3O2(aq); Fe (aq) PO4 (aq) FePO4(s)
3 3

2.49 mol Mg2 and 4.97 mol C2H3O2 (b) 2Na(aq) 2OH(aq) Cd2(aq) 2NO3(aq)
H O 2Na(aq) 2NO3(aq) Cd(OH)2(s)
(c) (NH4)2CrO4(s)
2
2NH4(aq) CrO42(aq);
2OH (aq) Cd (aq) Cd(OH)2(s)
2
6.24 mol NH4 and 3.12 mol CrO42
(c) No reaction occurs
H O
(d) NaHSO4(s)
2
Na(aq) HSO4(aq); (d) 2Ag(aq) SO42(aq) Ba2(aq) 2Cl(aq)
0.73 mol Na and 0.73 mol HSO4

2AgCl(s) BaSO4(s)
1L 3.20 mol HBr Total and net ionic equations are identical.
4.2 Moles of H 451 mL 4.4 2HNO3(aq) Ca(OH)2(aq) Ca(NO3)2(aq) 2H2O(l)
103 mL 1 L soln
2H(aq) 2NO3(aq) Ca2(aq) 2OH(aq)
1 mol H
1.44 mol H Ca2(aq) 2NO3(aq) 2H2O(l)
1 mol HBr
H (aq) OH (aq) H2O(l)
168 Chapter 4 The Major Classes of Chemical Reactions

Answers to Follow-up Problems (continued)

4.5 2HCl(aq) Ba(OH)2(aq) BaCl2(aq) 2H2O(l) 7.44102 mol Ca2 103 mL
Molarity of Ca2
Volume (L) of soln 2.50 mL milk 1L
1L 0.1016 mol HCl
50.00 mL HCl soln 3
2.98102 M Ca2
10 mL 1 L soln
2.98102 mol Ca2
1 mol Ba(OH)2 1 L soln (b) Conc. of Ca2 (g L)
1L
2 mol HCl 0.1292 mol Ba(OH)2
40.08 g Ca2
0.01966 L
1 mol Ca2
4.6 (a) O.N. of Sc 3; O.N. of O 2
(b) O.N. of Ga 3; O.N. of Cl 1 1.19 g Ca2

(c) O.N. of H 1; O.N. of P 5; O.N. of O 2 1L
(d) O.N. of I 3; O.N. of F 1 4.10 (a) Combination; redox:
4.7 (a) Fe is reducing agent; Cl2 is oxidizing agent. S8(s) 16F2(g) 8SF4(g)
(b) C2H6 is reducing agent; O2 is oxidizing agent. S8 is the reducing agent; F2 is the oxidizing agent.
(c) CO is reducing agent; I2O5 is oxidizing agent. (b) Double displacement; acid-base with gaseous product:
4.8 K2Cr2O7(aq) 14HI(aq) Na2SO3(aq) 2HCl(aq) 2NaCl(aq) SO2(g) H2O(l)
2KI(aq) 2CrI3(aq) 3I2(s) 7H2O(l) (c) Single displacement; redox:
4.9 (a) Moles of Ca2 3Ni(NO3)2(aq) 2Cr(s) 3Ni(s) 2Cr(NO3)3(aq)
1L 4.56103 mol KMnO4 Cr is the reducing agent; Ni(NO3)2 is the oxidizing agent.
6.53 mL soln 3
10 mL 1 L soln
5 mol CaC2O4 1 mol Ca2

2 mol KMnO4 1 mol CaC2O4
7.44105 mol Ca2

Problems
Problems with a colored number are answered at the back of 4.6 Which of the following best represents a volume from a
the text. Problem sections match the text and provide the solution of magnesium nitrate?
number(s) of relevant sample problems. Most offer concept
= magnesium ion = nitrate ion
review questions, skill-building exercises (written in similar
pairs), and problems in a relevant context. Following these are
comprehensive problems based on material from any section
and/or previous chapter.

The Role of Water as a Solvent

(Sample Problems 4.1 and 4.2) (1) (2) (3)

Concept Review Questions

4.7 Why do some ionic compounds dissolve in water and
4.1 What two factors cause water to be polar?
others do not?
4.2 What types of substances are most likely to be soluble in
4.8 Why are some covalent compounds soluble in water and
water?
others are not?
4.3 What must be present in an aqueous solution for it to
4.9 Some covalent compounds dissociate into ions when
conduct an electric current? What general classes of com-
they dissolve in water. What atom do these compounds have
pounds form solutions that conduct?
in their structures? What type of aqueous solution do they
4.4 What occurs on the molecular level when an ionic com-
form? Name three of these aqueous solutions.
pound dissolves in water?
4.5 Examine each of the following aqueous solutions and Skill-Building Exercises (paired)
determine which represents: (a) CaCl2 (b) Li2SO4 (c) NH4Br 4.10 State whether each of the following substances is likely
to be very soluble in water. Explain.
(a) Benzene, C6H6 (b) Sodium hydroxide
(c) Ethanol, CH3CH2OH (d) Potassium acetate
4.11 State whether each of the following substances is likely
to be very soluble in water. Explain.
(a) Lithium nitrate (b) Glycine, H2NCH2COOH
(1) (2) (3) (c) Hexane (d) Ethylene glycol, HOCH2CH2OH
Problems 169

4.12 State whether an aqueous solution of each of the fol- ing them with enough Na ions to maintain the same num-
lowing substances conducts an electric current. Explain your ber of positive charges in the solution. If 1.0103 L hard
reasoning. (a) Sodium iodide (b) Hydrogen bromide water is 0.015 M Ca2 and 0.0010 M Fe3, how many moles
4.13 State whether an aqueous solution of each of the fol- of Na are needed to replace these ions?
lowing substances conducts an electric current. Explain your
reasoning. (a) Potassium hydroxide (b) Glucose, C6H12O6 Precipitation Reactions and Acid-Base
4.14 How many total moles of ions are released when each
Reactions
of the following samples dissolves completely in water? (Sample Problems 4.3 to 4.5)
(a) 0.25 mol NH4Cl (b) 26.4 g Ba(OH)28H2O
Concept Review Questions
(c) 1.781020 formula units of LiCl
4.24 When two solutions of ionic compounds are mixed, a
4.15 How many total moles of ions are released when each
reaction occurs only if ions are removed from solution to
of the following samples dissolves completely in water?
form product. What are three ways in which this removal
(a) 0.805 mol Cs2SO4 (b) 1.55103 g Ca(NO3)2
can occur? What type of reaction is involved in each case?
(c) 3.851027 formula units of Sr(HCO3)2
4.25 Why do some pairs of ions form precipitates and others
4.16 How many total moles of ions are released when each do not?
of the following samples dissolves completely in water? 4.26 Which ions do not appear in a net ionic equation?
(a) 0.15 mol Na3PO4 (b) 47.9 g NiBr23H2O Why?
(c) 4.231022 formula units of FeCl3 4.27 Use Table 4.1 to determine which of the following
4.17 How many total moles of ions are released when each combinations leads to a reaction. How can you identify the
of the following samples dissolves completely in water? spectator ions in the reaction?
(a) 0.382 mol K2HPO4 (b) 6.80 g MgSO47H2O (a) Calcium nitrate(aq) potassium chloride(aq)
(c) 6.1881021 formula units of NiCl2 (b) Sodium chloride(aq) lead(II) nitrate(aq)
4.28 Is the total ionic equation the same as the net ionic
4.18 How many ions of each type are present in the follow-
equation for the reaction between Sr(OH)2(aq) and
ing aqueous solutions?
H2SO4(aq)? Explain.
(a) 95.5 mL of 2.45 M aluminum chloride
4.29 State a general equation for a neutralization reaction.
(b) 2.50 L of a solution containing 4.59 g/L sodium sulfate
4.30 (a) Name three common strong acids.
(c) 80.5 mL of a solution containing 2.681022 formula
(b) Name three common strong bases.
units of magnesium bromide per liter
(c) What is a characteristic behavior of a strong acid or a
4.19 How many ions of each type are present in the follow-
strong base?
ing aqueous solutions?
4.31 (a) Name three common weak acids.
(a) 3.8 mL of 1.88 M magnesium chloride
(b) Name one common weak base.
(b) 345 mL of a solution containing 4.22 g/L aluminum
(c) What is the major difference between a weak acid and a
sulfate
strong acid or between a weak base and a strong base, and
(c) 2.66 L of a solution containing 6.631021 formula units
what experiment would you perform to test it?
of lithium nitrate per liter
4.32 Do either of the following reactions go to completion?
4.20 How many moles of H ions are present in the follow- If so, what factor(s) drives each to completion?
ing aqueous solutions? (a) MgSO3(s) 2HCl(aq) MgCl2(aq) SO2(g) H2O(l)
(a) 0.140 L of 2.5 M perchloric acid (b) 3Ba(OH)2(aq) 2H3PO4(aq) Ba3(PO4)2(s) 6H2O(l)
(b) 6.8 mL of 0.52 M nitric acid 4.33 The net ionic equation for the aqueous neutralization
(c) 2.5 L of 0.056 M hydrochloric acid reaction between acetic acid and sodium hydroxide is differ-
4.21 How many moles of H ions are present in the follow- ent from the equation for hydrochloric acid and sodium
ing aqueous solutions? hydroxide. Explain by writing balanced net ionic equations.
(a) 1.4 L of 0.48 M hydrobromic acid
(b) 47 mL of 1.8 M hydriodic acid Skill-Building Exercises (paired)
(c) 425 mL of 0.27 M nitric acid 4.34 When each of the following pairs of aqueous solutions
is mixed, does a precipitation reaction occur? If so, write the
Problems in Context
formula and name of the precipitate:
4.22 In laboratory studies of ocean-dwelling organisms,
(a) Sodium nitrate copper(II) sulfate
marine biologists use salt mixtures that simulate the ion
(b) Ammonium iodide silver nitrate
concentrations in seawater. A 1.00-kg sample of simulated
4.35 When each of the following pairs of aqueous solutions
seawater is prepared by mixing 26.5 g NaCl, 2.40 g MgCl2,
is mixed, does a precipitation reaction occur? If so, write the
3.35 g MgSO4, 1.20 g CaCl2, 1.05 g KCl, 0.315 g NaHCO3,
formula and name of the precipitate:
and 0.098 g NaBr in distilled water.
(a) Potassium carbonate barium hydroxide
(a) If the density of this solution is 1.04 g/cm3, what is the
(b) Aluminum nitrate sodium phosphate
molarity of each ion?
(b) What is the total molarity of alkali metal ions? 4.36 When each of the following pairs of aqueous solutions
(c) What is the total molarity of alkaline earth metal ions? is mixed, does a precipitation reaction occur? If so, write the
(d) What is the total molarity of anions? formula and name of the precipitate:
4.23 Water softeners remove metal ions such as Fe2, (a) Potassium chloride iron(II) nitrate
Fe3, Ca2, and Mg2 (which make water hard) by replac- (b) Ammonium sulfate barium chloride
170 Chapter 4 The Major Classes of Chemical Reactions

4.37 When each of the following pairs of aqueous solutions reading was 39.21 mL. What was the molarity of the base
is mixed, does a precipitation reaction occur? If so, write the solution?
formula and name of the precipitate: 4.50 The mass percent of Cl in a seawater sample is deter-
(a) Sodium sulfide nickel(II) sulfate mined by titrating 25.00 mL seawater with AgNO3 solution,
(b) Lead(II) nitrate potassium bromide causing a precipitation reaction. An indicator is used to de-
tect the end point, which occurs when free Ag ion is pre-
4.38 Complete the following precipitation reactions with
sent in solution after all the Cl is consumed. If 43.63 mL of
balanced molecular, total ionic, and net ionic equations, and
0.3020 M AgNO3 is required to reach the end point, what is
identify the spectator ions:
the mass percent of Cl in the seawater? (d of seawater
(a) Hg2(NO3)2(aq) KI(aq)
1.04 g/mL.)
(b) FeSO4(aq) Ba(OH)2(aq)
4.51 Aluminum sulfate, known as cake alum, has a remark-
4.39 Complete the following precipitation reactions with
ably wide range of uses, from dyeing leather and cloth to
balanced molecular, total ionic, and net ionic equations, and
purifying sewage. In aqueous solution, it reacts with base to
identify the spectator ions:
form a white precipitate. (a) Write balanced total and net
(a) CaCl2(aq) Cs3PO4(aq)
ionic equations for its reaction with aqueous NaOH.
(b) Na2S(aq) ZnSO4(aq)
(b) What mass of precipitate forms when 135.5 L of 0.633 M
4.40 Complete the following acid-base reactions with bal- NaOH is added to 517 mL of a solution that contains 12.8 g
anced molecular, total ionic, and net ionic equations, and aluminum sulfate per liter?
identify the spectator ions:
(a) Potassium hydroxide(aq) hydriodic acid(aq) Oxidation-Reduction (Redox) Reactions
(b) Ammonia(aq) hydrochloric acid(aq) (Sample Problems 4.6 to 4.9)
4.41 Complete the following acid-base reactions with bal- Concept Review Questions
anced molecular, total ionic, and net ionic equations, and 4.52 Describe how to determine the oxidation number of
identify the spectator ions: sulfur in (a) H2S and (b) SO3.
(a) Cesium hydroxide(aq) nitric acid(aq) 4.53 Is the following a redox reaction? Explain.
(b) Calcium hydroxide(aq) acetic acid(aq)
NH3(aq) HCl(aq) NH4Cl(aq)
4.42 Limestone (calcium carbonate) is insoluble in water but 4.54 Explain why an oxidizing agent undergoes reduction.
dissolves when a hydrochloric acid solution is added. Why? 4.55 Why must every redox reaction involve an oxidizing
Write balanced total ionic and net ionic equations, showing agent and a reducing agent?
hydrochloric acid as it actually exists in water and the reac- 4.56 In which of the following equations does sulfuric acid
tion as a proton-transfer process. act as an oxidizing agent? In which does it act as an acid?
4.43 Zinc hydroxide is insoluble in water but dissolves when Explain.
a nitric acid solution is added. Why? Write balanced total (a) 4H(aq) SO42(aq) 2NaI(s)
ionic and net ionic equations, showing nitric acid as it actu- 2Na(aq) I2(s) SO2(g) 2H2O(l)
ally exists in water and the reaction as a proton-transfer
(b) BaF2(s) 2H (aq) SO42(aq)
process. 2HF(aq) BaSO4(s)
4.44 If 35.0 mL lead(II) nitrate solution reacts completely 4.57 Identify the oxidizing agent and the reducing agent in
with excess sodium iodide solution to yield 0.628 g precipi- the following reaction, and explain your answer:
tate, what is the molarity of lead(II) ion in the original solu- 8NH3(g) 6NO2(g) 7N2(g) 12H2O(l)
tion?
Skill-Building Exercises (paired)
4.45 If 25.0 mL silver nitrate solution reacts with excess
4.58 Give the oxidation number of carbon in each of the
potassium chloride solution to yield 0.842 g precipitate,
following: (a) CF2Cl2 (b) Na2C2O4 (c) HCO3 (d) C2H6
what is the molarity of silver ion in the original solution?
4.59 Give the oxidation number of bromine in each of the
4.46 If 15.98 mL of a standard 0.1080 M KOH solution re- following: (a) KBr (b) BrF3 (c) HBrO3 (d) CBr4
acts with 52.00 mL of CH3COOH solution, what is the mo- 4.60 Give the oxidation number of nitrogen in each of the
larity of the acid solution? following: (a) NH2OH (b) N2H4 (c) NH4 (d) HNO2
4.47 If 26.35 mL of a standard 0.1650 M NaOH solution is 4.61 Give the oxidation number of sulfur in each of the
required to neutralize 35.00 mL H2SO4, what is the molarity following: (a) SOCl2 (b) H2S2 (c) H2SO3 (d) Na2S
of the acid solution?
4.62 Give the oxidation number of arsenic in each of the
Problems in Context following: (a) AsH3 (b) H3AsO4 (c) AsCl3
4.48 An auto mechanic spills 85 mL of 2.6 M H2SO4 solution 4.63 Give the oxidation number of phosphorus in each of
from a rebuilt auto battery. How many milliliters of 2.5 M the following: (a) H2P2O72 (b) PH4 (c) PCl5
NaHCO3 must be poured on the spill to react completely
4.64 Give the oxidation number of manganese in each of
with the sulfuric acid?
4.49 Sodium hydroxide is used extensively in acid-base
the following: (a) MnO42 (b) Mn2O3 (c) KMnO4
4.65 Give the oxidation number of chromium in each of the
titrations because it is a strong, inexpensive base. A sodium
hydroxide solution was standardized by titrating 25.00 mL of following: (a) CrO3 (b) Cr2O72 (c) Cr2(SO4)3
0.1528 M standard hydrochloric acid. The initial buret read- 4.66 Identify the oxidizing agent and the reducing agent in
ing of the sodium hydroxide was 2.24 mL and the final each of the following:
Problems 171

(a) 5H2C2O4(aq) 2MnO4(aq) 6H(aq) (a) How many moles of MnO4 were required for the titra-
2Mn2(aq) 10CO2(g) 8H2O(l) tion if 43.2 mL of 0.105 M KMnO4 was needed to reach the
(b) 3Cu(s) 8H (aq) 2NO3(aq)

end point?
3Cu2(aq) 2NO(g) 4H2O(l) (b) How many moles of H2O2 were present in the 13.8-g
4.67 Identify the oxidizing agent and the reducing agent in sample of bleach?
each of the following: (c) How many grams of H2O2 were in the sample?
(a) Sn(s) 2H(aq) Sn2(aq) H2(g) (d) What is the mass percent H2O2 in the sample?
(b) 2H(aq) H2O2(aq) 2Fe2(aq) (e) What is the reducing agent in the redox reaction?
2Fe3(aq) 2H2O(l) 4.75 The beakers represent the aqueous reaction of AgNO3
and NaCl. If silver ions are gray, what colors are used to
4.68 Identify the oxidizing agent and the reducing agent in represent NO3, Na, and Cl? Write molecular, total ionic,
each of the following: and net ionic equations for the reaction.
(a) 8H(aq) 6Cl(aq) Sn(s) 4NO3(aq)
SnCl62(aq) 4NO2(g) 4H2O(l)
(b) 2MnO4(aq) 10Cl(aq) 16H(aq)
5Cl2(g) 2Mn2(aq) 8H2O(l) +

4.69 Identify the oxidizing agent and the reducing agent in

each of the following:
(a) 8H(aq) Cr2O72(aq) 3SO32(aq)
2Cr3(aq) 3SO42(aq) 4H2O(l) 4.76 A persons blood alcohol (C2H5OH) level can be deter-
(b) NO3(aq) 4Zn(s) 7OH(aq) 6H2O(l) mined by titrating a sample of blood plasma with a potas-
4Zn(OH)42(aq) NH3(aq) sium dichromate solution. The balanced equation is

4.70 Discuss each conclusion from a study of redox reactions:

16H(aq) 2Cr2O72(aq) C2H5OH(aq)
(a) The sulfide ion functions only as a reducing agent. 4Cr3(aq) 2CO2(g) 11H2O(l)
(b) The sulfate ion functions only as an oxidizing agent. If 35.46 mL of 0.05961 M Cr2O72 is required to titrate
(c) Sulfur dioxide functions as either an oxidizing or a re- 28.00 g plasma, what is the mass percent of alcohol in the
ducing agent. blood?
4.71 Discuss each conclusion from a study of redox reactions:
Counting Reactants and Products in
(a) The nitride ion functions only as a reducing agent.
Precipitation, Acid-Base, and
(b) The nitrate ion functions only as an oxidizing agent.
Redox Processes
(c) The nitrite ion functions as either an oxidizing or a re-
(Sample Problem 4.10)
ducing agent.
Concept Review Questions
4.72 Use the oxidation number method to balance the fol-
4.77 What is the name of the type of reaction that leads to
lowing equations by placing coefficients in the blanks. Iden-
the following?
tify the reducing and oxidizing agents:
(a) An increase in the number of substances
(a) __HNO3(aq) __K2CrO4(aq) __Fe(NO3)2(aq)
(b) A decrease in the number of substances
__KNO3(aq) __Fe(NO3)3(aq) __Cr(NO3)3(aq) __H2O(l)
(c) No change in the number of substances
(b) __HNO3(aq) __C2H6O(l) __K2Cr2O7(aq)
4.78 Why do decomposition reactions typically have com-
__KNO3(aq) __C2H4O(l) __H2O(l) __Cr(NO3)3(aq)
pounds as reactants, whereas combination and displacement
(c) __HCl(aq) __NH4Cl(aq) __K2Cr2O7(aq)
reactions have either elements or compounds?
__KCl(aq) __CrCl3(aq) __N2(g) __H2O(l)
4.79 Which of the three types of reactions discussed in this
(d) __KClO3(aq) __HBr(aq)
section commonly produce one or more compounds?
__Br2(l) __H2O(l) __KCl(aq)
4.80 Give an example of a combination reaction that is a
4.73 Use the oxidation number method to balance the fol-
redox reaction. Give an example of a combination reaction
lowing equations by placing coefficients in the blanks. Iden-
that is not a redox reaction.
tify the reducing and oxidizing agents:
4.81 Are all combustion reactions redox reactions? Explain.
(a) __HCl(aq) __FeCl2(aq) __H2O2(aq)
__FeCl3(aq) __H2O(l) Skill-Building Exercises (paired)
(b) __I2(s) __Na2S2O3(aq) __Na2S4O6(aq) __NaI(aq) 4.82 Balance each of the following, classify it as a combina-
(c) __HNO3(aq) __KI(aq) tion, decomposition, or displacement reaction, and state
__NO(g) __I2(s) __H2O(l) __KNO3(aq) whether it is a redox process:
(d) __PbO(s) __NH3(aq) __N2(g) __H2O(l) __Pb(s) (a) Ca(s) H2O(l) Ca(OH)2(aq) H2(g)
(b) NaNO3(s) NaNO2(s) O2(g)
Problems in Context (c) C2H2(g) H2(g) C2H6(g)
4.74 The active agent in many hair bleaches is hydrogen 4.83 Balance each of the following, classify it as a combina-
peroxide. The amount of hydrogen peroxide in 13.8 g hair tion, decomposition, or displacement reaction, and state
bleach was determined by titration with a standard potas- whether it is a redox process:
sium permanganate solution: (a) HI(g) H2(g) I2(g)
2MnO4(aq) 5H2O2(aq) 6H(aq) (b) Zn(s) AgNO3(ag) Zn(NO3)2(aq) Ag(s)
5O2(g) 2Mn2(aq) 8H2O(l) (c) NO(g) O2(g) N2O4(l)
172 Chapter 4 The Major Classes of Chemical Reactions

4.84 Balance each of the following, classify it as a combina- 4.94 How many grams of O2 can be prepared from the com-
tion, decomposition, or displacement reaction, and state plete decomposition of 4.27 kg HgO? Name and calculate the
whether it is a redox process: mass (in kg) of the other product.
(a) Sb(s) Cl2(g) SbCl3(s) 4.95 How many grams of lime (CaO) can be produced from
(b) AsH3(g) As(s) H2(g) the complete decomposition of 114.52 g limestone (CaCO3)?
(c) C2H5OH(l) C2H4(g) H2O(g) Name and calculate the mass (in grams) of the other
4.85 Balance each of the following, classify it as a combina- product.
tion, decomposition, or displacement reaction, and state
whether it is a redox process: 4.96 In a combination reaction, 1.62 g lithium is mixed with
(a) Mg(s) H2O(g) Mg(OH)2(s) H2(g) 6.00 g oxygen.
(b) Cr(NO3)3(aq) Al(s) Al(NO3)3(aq) Cr(s) (a) Which reactant is present in excess?
(c) PF3(g) F2(g) PF5(g) (b) How many moles of product are formed?
(c) After reaction, how many grams of each reactant and
4.86 Complete the following general reactions, and write a product are present?
specific balanced equation to exemplify each: 4.97 In a combination reaction, 2.22 g magnesium is heated
(a) Metal oxygen with 3.75 g nitrogen.
(b) Nonmetal halide halogen (a) Which reactant is present in excess?
(c) Nonmetal oxide water (b) How many moles of product are formed?
(d) Metal hydroxide (c) After reaction, how many grams of each reactant and
4.87 Complete the following general reactions, and write a product are present?
specific balanced equation to exemplify each:
(a) Nonmetal nonmetal 4.98 A mixture of KClO3 and KCl with a mass of 0.900 g
(b) Metal oxide nonmetal oxide was heated to produce O2. After heating, the mass of residue
(c) Metal carbonate was 0.700 g. Assuming all the KClO3 decomposed to KCl
(d) Acid base and O2, calculate the mass percent of KClO3 in the original
mixture.
4.88 Predict the product(s), write a balanced equation, and
4.99 A mixture of CaCO3 and CaO weighing 0.693 g was
state whether each of the following is a redox reaction:
heated to produce CO2. After heating, the remaining solid
(a) Ca(s) Br2(l)
weighed 0.508 g. Assuming all the CaCO3 decomposed to
(b) Ag2O(s)
CaO and CO2, calculate the mass percent of CaCO3 in the
(c) Mn(s) Cu(NO3)2(aq) original mixture.
4.89 Predict the product(s), write a balanced equation, and
state whether each of the following is a redox reaction:
Problems in Context
(a) Ca(OH)2(aq) HCl(aq)
electricity 4.100 Before arc welding
(b) LiCl(l) was developed, a displace-
(c) SnCl2(aq) Co(s) ment reaction involving
4.90 Predict the product(s), write a balanced equation, and aluminum and iron(III)
state whether each of the following is a redox reaction: oxide was commonly used
(a) N2(g) H2(g) to produce molten iron
(b) NaClO3(s) (the thermite process; see
(c) Ba(s) H2O(l) photo). This reaction was
4.91 Predict the product(s), write a balanced equation, and
used, for example, to
state whether each of the following is a redox reaction: connect sections of iron
(a) KOH(aq) HClO4(aq) railroad track. Calculate
(b) S8(s) O2(g) the mass of molten iron
(c) BaCl2(aq) Na2SO4(aq) produced when 1.00 kg
aluminum reacts with
4.92 Predict the product(s), write a balanced equation, and 2.00 mol iron(III) oxide.
state whether each of the following is a redox reaction: 4.101 One of the first steps in the enrichment of uranium
(a) Cesium iodine for use in nuclear power plants involves a displacement
(b) Aluminum aqueous manganese(II) sulfate reaction between UO2 and aqueous HF:
(c) Sulfur dioxide oxygen
UO2(s) 4HF(aq) UF4(s) 2H2O(l)
(d) Carbon dioxide barium oxide
(e) Write a balanced net ionic equation for (b). How many liters of 6.50 M HF are needed to react with 3.25
4.93 Predict the product(s), write a balanced equation, and kg UO2?
state whether each of the following is a redox reaction: 4.102 The field of sports medicine has become an important
(a) Calcium oxide water specialty, with physicians routinely treating athletes and
(b) Phosphorus trichloride chlorine dancers. Ethyl chloride, a local anesthetic commonly used
(c) Zinc hydrobromic acid for simple injuries, is the product of the combination of
(d) Aqueous potassium iodide bromine ethylene with hydrogen chloride:
(e) Write a balanced net ionic equation for (d). C2H4(g) HCl(g) C2H5Cl(g)
Problems 173

If 0.100 kg C2H4 and 0.100 kg HCl react, (b) Measurements show an increase from 3.3 mg iron to 49
(a) How many molecules of gas (reactants plus products) are mg iron per 12-cup (125 g) serving during the slow prepara-
present when the reaction is complete? tion of tomato sauce in a cast-iron pot. How many ferrous
(b) How many moles of gas are present when half the prod- ions are present in a 26-oz (737 g) jar of tomato sauce?
uct forms? 4.110 Limestone (CaCO3) is used to remove acidic pollu-
4.103 Iron reacts rapidly with chlorine gas to form Com- tants from smokestack flue gases in a sequence of decompo-
pound A, a reddish-brown ionic compound, which contains sition-combination reactions. The limestone is heated to
iron in the higher of its two common oxidation states (see form lime (CaO), which reacts with sulfur dioxide to form
photo). Strong heating decomposes Compound A to Com- calcium sulfite. Assuming a 70.% yield in the overall reac-
pound B, another ionic compound, which contains iron in tion, what mass of limestone is required to remove all the
the lower of its two oxidation states. When Compound A is sulfur dioxide formed by the combustion of 8.5104 kg coal
formed by the reaction of 50.6 g Fe and 83.8 g Cl2 and then that is 0.33 mass % sulfur?
heated, how much Compound B forms? 4.111 The brewing industry uses yeast microorganisms to
convert glucose to ethanol for wine and beer. The baking
industry uses the carbon dioxide these single-celled fungi
produce to make bread rise:
yeast
C6H12O6(s) 2C2H5OH(l) 2CO2( g)
How many grams of ethanol can be produced from the de-
composition of 10.0 g glucose? What volume of CO2 is pro-
duced? (Assume 1 mol of gas occupies 22.4 L under the
conditions used.)
4.112 A chemical engineer determines the mass percent of
iron in an ore sample by converting the Fe to Fe2 in acid
and then titrating the Fe2 with MnO4. A 1.1081-g sample
was dissolved in acid and then titrated with 39.32 mL of
0.03190 M KMnO4. The balanced equation is
8H(aq) 5Fe2(aq) MnO4(aq)
5Fe3(aq) Mn2(aq) 4H2O(l)
Reversible Reactions: An Introduction to Calculate the mass percent of iron in the ore.
Chemical Equilibrium 4.113 Mixtures of CaCl2 and NaCl are used for salting roads
to prevent ice formation. A dissolved 1.9348-g sample of
Concept Review Questions such a mixture was analyzed by using excess Na2C2O4 to
4.104 Why is the equilibrium state called dynamic? completely precipitate the Ca2 as CaC2O4. The CaC2O4 was
4.105 In a decomposition reaction involving a gaseous prod- separated from the solution and then dissolved with sulfuric
uct, what must be done for the reaction to reach equilibrium? acid. The resulting H2C2O4 was titrated with 37.68 mL of
4.106 Describe what happens on the molecular level when 0.1019 M KMnO4 solution.
acetic acid dissolves in water. (a) Write the balanced net ionic equation for the precipita-
4.107 When either a mixture of NO and Br2 or pure nitrosyl tion reaction.
bromide (NOBr) is placed in a reaction vessel, the product (b) Write the balanced net ionic equation for the titration
mixture contains NO, Br2, and NOBr. Explain. reaction. (See Sample Problem 4.9.)
Problems in Context (c) What is the oxidizing agent?
4.108 Ammonia is produced by the millions of tons annu- (d) What is the reducing agent?
ally for use as a fertilizer. It is commonly made from N2 and (e) Calculate the mass percent of CaCl2 in the original
H2 by the Haber process. Because the reaction reaches equi- sample.
librium before going completely to product, the stoichiomet- 4.114 Nickel chloride solution is used industrially for plating
ric amount of ammonia is not obtained. At a particular zinc and other metals. The solution is shipped in tin-lined
temperature and pressure, 10.0 g H2 reacts with 20.0 g N2 to iron drums. Explain with balanced equations why the drums
form ammonia. When equilibrium is reached, 15.0 g NH3 must be lined. What would happen to solution stored in an
has formed. unlined drum?
(a) Calculate the percent yield. 4.115 Precipitation reactions are often used to prepare use-
(b) How many moles of N2 and H2 are present at equilibrium? ful ionic compounds. For example, thousands of tons of
silver bromide are prepared annually for use in making
Comprehensive Problems black-and-white photographic film. (a) What mass (in kilo-
Problems with an asterisk (*) are more challenging. grams) of silver bromide forms when 5.85 m3 of 1.68 M
4.109 Nutritional biochemists have known for decades that potassium bromide reacts with 3.51 m3 of 2.04 M silver
acidic foods cooked in cast-iron cookware can supply signifi- nitrate? (b) After the solid silver bromide is removed, what
cant amounts of dietary (ferrous) iron. ions are present in the remaining solution? Determine the
(a) Write a balanced net ionic equation, with oxidation molarity of each ion. (Assume the total volume is the sum of
numbers, that supports this fact. the reactant volumes.)
174 Chapter 4 The Major Classes of Chemical Reactions

4.116 The flask (right) depicts the prod- 4.123 Use the oxidation number method to balance the
ucts of the titration of 25 mL sulfuric following reactions by placing coefficients in the blanks.
acid with 25 mL sodium hydroxide. Identify the reducing and oxidizing agents:
(a) Write balanced molecular, total (a) __CrO42(aq) __HSnO2(aq) __H2O(l)
ionic, and net ionic equations for the __CrO2(aq) __HSnO3(aq) __OH(aq)
reaction. (b) __KMnO4(aq) __NaNO2(aq) __H2O(l)
(b) If each orange sphere represents __MnO2(s) __NaNO3(aq) __KOH(aq)
0.010 mol sulfate ion, how many moles (c) __I(aq) __O2(g) __H2O(l) __I2(s) __OH(aq)
of acid and of base reacted? 4.124 Sodium peroxide (Na2O2) is often used in self-con-
(c) What are the molarities of the acid tained breathing devices, such as those used in fire emergen-
and the base? cies, because it reacts with exhaled CO2 to form Na2CO3 and
4.117 To find the mass percent of dolomite [CaMg(CO3)2] in O2. How many liters of respired air can react with 80.0 g
a soil sample, a geochemist titrates 12.86 g of the soil with Na2O2 if each liter of respired air contains 0.0720 g CO2?
33.56 mL of 0.2516 M HCl. What is the mass percent of 4.125 Magnesium is used in many lightweight alloys, in-
dolomite in the soil? cluding those in airplane bodies. The metal is obtained from
4.118 The calcium carbonate impurity in a sample of phos- seawater in an industrial process that includes precipitation,
phate rock is removed by treatment with hydrochloric acid; neutralization, evaporation, and electrolysis. How many
the products are carbon dioxide, water, and aqueous calcium kilograms of magnesium can be obtained from 1.00 km3
chloride. When 15.5 g of the rock is treated with excess seawater if the initial Mg2 concentration is 0.13% by mass?
hydrochloric acid, 1.81 g carbon dioxide is formed. Calculate (d of seawater 1.04 g/mL.)
the mass percent of calcium carbonate in the rock. *4.126 A typical formulation for window glass is 75% SiO2,
*4.119 When zinc metal is treated with dilute nitric acid, the 15% Na2O, and 10.% CaO by mass. What masses of sand
reaction produces nitrogen gas, water, and aqueous zinc (SiO2), sodium carbonate, and calcium carbonate must be
nitrate. Write a balanced equation for the reaction. combined to produce 1.00 kg glass after carbon dioxide is
4.120 Complete each of the following reactions and write driven off by thermal decomposition of the carbonates?
net ionic equations for them: 4.127 The salinity of a solution is defined as the grams of
1. NaOH(aq) HCl(aq) total salts per kilogram of solution. An agricultural chemist
2. KOH(aq) HNO3(aq) uses a solution whose salinity is 35.0 g/kg to test the effect of
3. Ba(OH)2(aq) 2HBr(aq) irrigating farmland with high-salinity river water. The two
(a) What do you conclude from these equations about the solutes are NaCl and MgSO4, and there are twice as many
nature of the reactants? moles of NaCl as MgSO4. What masses of NaCl and MgSO4
(b) What are the spectator ions in each reaction? are contained in 1.00 kg of the solution?
4.121 Use the oxidation number method to balance the *4.128 Thyroxine (C15H11I4NO4) is a hormone synthesized
following equations by placing coefficients in the blanks. by the thyroid gland and used to control many metabolic
Identify the reducing and oxidizing agents: functions in the body. A physiologist determines the mass %
(a) __KOH(aq) __H2O2(aq) __Cr(OH)3(s) of thyroxine in a thyroid extract by igniting 0.4332 g of
__K2CrO4(aq) __H2O(l) extract with sodium carbonate, which converts the iodine to
(b) __MnO4(aq) __ClO2(aq) __H2O(l) iodide. The iodide is dissolved in water, and bromine and
__MnO2(s) __ClO4(aq) __OH(aq) hydrochloric acid are added, which convert the iodide to
(c) __KMnO4(aq) __Na2SO3(aq) __H2O(l) iodate.
__MnO2(s) __Na2SO4(aq) __KOH(aq) (a) How many moles of iodate are produced per mole of
4.122 In a key reaction during the industrial production of thyroxine?
pig iron, a molten silicate slag forms in the blast furnace (b) Excess bromine is boiled off and more iodide is added,
when sand (silicon dioxide) and lime (calcium oxide) react which reacts as follows:
(see photo). (a) Write a balanced equation for this reaction. IO3(aq) H(aq) I(aq)
(b) Is this a redox reaction? Show with oxidation numbers. I2(aq) H2O(l) [unbalanced]
How many moles of iodine are produced per mole of thyrox-
ine? (Hint: Be sure to balance the charges as well as the
atoms.) What are the oxidizing and reducing agents in the
reaction?
(c) The iodine reacts completely with 17.23 mL of 0.1000 M
thiosulfate as follows:
I2(aq) S2O32(aq) I(aq) S4O62(aq) [unbalanced]
What is the mass % of thyroxine in the thyroid extract?
4.129 Carbon dioxide is removed from the atmosphere of
space capsules by reaction with a solid metal hydroxide. The
products are water and the metal carbonate.
(a) Calculate the mass of CO2 that can be removed by reac-
tion with 3.50 kg lithium hydroxide.
Problems 175

(b) How many grams of CO2 can be removed by 1.00 g of *4.133 In 1997, at the United Nations Conference on Cli-
each of the following: lithium hydroxide, magnesium hy- mate Change, the major industrial nations agreed to expand
droxide, and aluminum hydroxide? their research efforts to develop renewable sources of car-
*4.130 Calcium dihydrogen phosphate, Ca(H2PO4)2, and bon-based fuels. For more than a decade, Brazil has been
sodium hydrogen carbonate, NaHCO3, are ingredients of engaged in a program to replace gasoline with ethanol de-
baking powder that react with each other to produce CO2, rived from the root crop manioc (cassava).
which causes dough or batter to rise: (a) Write separate balanced equations for the complete com-
Ca(H2PO4)2(s) NaHCO3(s) bustion of ethanol (C2H5OH) and of gasoline (represented by
CO2(g) H2O(g) CaHPO4(s) Na2HPO4(s) the formula C8H18).
[unbalanced] (b) What mass of oxygen is required to burn completely
1.00 L of a mixture that is 90.0% gasoline (d 0.742 g/mL)
If the baking powder contains 31% NaHCO3 and 35%
and 10.0% ethanol (d 0.789 g/mL) by volume?
Ca(H2PO4)2 by mass,
(c) If 1.00 mol O2 occupies 22.4 L, what volume of O2 is
(a) How many moles of CO2 are produced from 1.00 g bak-
needed to burn 1.00 L of the mixture?
ing powder?
(d) Air is 20.9% O2 by volume. What volume of air is
(b) If 1 mol CO2 occupies 37.0 L at 350F (a typical baking
needed to burn 1.00 L of the mixture?
temperature), what volume of CO2 is produced from 1.00 g
*4.134 When NaCl(s) dissolves in water, the ions separate;
baking powder?
when the water evaporates, NaCl(s) re-forms. When HCl(g)
4.131 During the process of developing black-and-white
dissolves in water, a covalent bond breaks; when the water
film, unexposed silver bromide is removed in a displacement
evaporates, HCl(g) re-forms. Are either or both of these
reaction with sodium thiosulfate solution:
chemical changes? Discuss.
AgBr(s) 2Na2S2O3(aq) Na3Ag(S2O3)2(aq) NaBr(aq) 4.135 One of the molecules responsible for atmospheric
What volume of 0.105 M Na2S2O3 solution is needed to ozone depletion is the refrigerant and aerosol propellant
remove 2.66 g AgBr from a roll of film? Freon-12 (CF2Cl2). It can be prepared commercially in a
4.132 Ionic hydrates lose sequence of two reactions:
their waters of hydration 1. A combination reaction between hydrogen and fluorine
when thermally decom- gases
posed. When 25.36 g of 2. A displacement reaction between the product of the first
hydrated copper(II) sulfate reaction and liquid carbon tetrachloride. Hydrogen chloride
is heated, it forms 16.21 g gas also forms.
of anhydrous copper(II) (a) Write balanced equations for the two reactions.
sulfate (see photo). What is (b) What is the maximum mass (in kg) of Freon-12 that can
the formula of the hydrate? be produced from 0.760 kg fluorine?