Introduction to Reactions

in Aqueous Solutions
CONTENTS
5
5-1 The Nature of
Aqueous Solutions
5-2 Precipitation Reactions
5-3 Acid Base Reactions
5-4 Oxidation Reduction
Reactions: Some
General Principles
5-5 Balancing
Oxidation Reduction
Equations
5-6 Oxidizing and
Reducing Agents
5-7 Stoichiometry of
Reactions in Aqueous
Solutions: Titrations

When clear, colorless aqueous solutions of cobalt(II) chloride and sodium hydroxide
are mixed, a blue cloud of solid cobalt(II) hydroxide is formed. Such precipitation
reactions are one of the three types of reactions considered in this chapter.

M
ost reactions in the general chemistry laboratory are carried out
in aqueous solutions solutions for which water is the solvent.
Aqueous solutions provide a convenient way of bringing
together accurately measured amounts of reactants, and, not surpris-
ingly, aqueous solutions feature prominently in many methods of chem-
ical analysis. In this chapter, we will explore three different classes of
reactions that occur in aqueous solutions precipitation, acid base, and
oxidation reduction reactions with the goal of understanding the
nature of the substances involved, the changes that occur in these sub-
stances, and the way each reaction can be used in the laboratory for ana-
lyzing samples.
Precipitation, the formation of a solid when solutions are mixed, is
probably the most common evidence of a chemical reaction that general
chemistry students see. A practical application of precipitation is in deter-
mining the presence of certain ions in solution. If, for example, we are
uncertain whether the clear, colorless liquid in an unlabeled bottle is a bar-
ium nitrate or a barium chloride solution, we can easily find out by adding
a few drops of silver nitrate solution to a small sample of the liquid. If a
white solid forms, the sample is a barium chloride solution; if nothing
151
152 Chapter 5 Introduction to Reactions in Aqueous Solutions

happens, it is barium nitrate. The Ag + from the silver nitrate and the Cl - from
the barium chloride combine to produce an insoluble precipitate of AgCl(s).

Mg1OH221s2 is insoluble in water but soluble in hydrochloric acid, HCl(aq), as

Precipitation reactions are the first reaction type we will study in this chapter.

a result of an acid base reaction. This is the reaction by which milk of magne-
sia neutralizes excess stomach acid. Magnesium hydroxide is a base, and
acid base reactions are the second class of reactions presented in this chapter.
The third class of reactions is oxidation reduction reactions, which are found
in all aspects of life, from reactions in organisms to processes for manufactur-
ing chemicals, to such practical matters as bleaching fabrics, purifying water,
and destroying toxic chemicals.

(a)
5-1 The Nature of Aqueous Solutions
Let s try to form a mental image of a solution at the molecular level. The solvent
molecules, which are rather tightly packed, greatly outnumber all other mole-
cules. Water is the solvent in an aqueous solution, and our mental image of
water might look something like Figure 5-1(a). Solute particles molecules or
ions are present in much smaller number and are randomly distributed
(b)
among the solvent molecules. Our mental image of an aqueous solution of air
FIGURE 5-1
might look something like Figure 5-1(b).
Molecular view of water
and an aqueous solution Because we will encounter aqueous solutions of ions throughout this
of air chapter, it is useful to examine the nature of such solutions in a bit more
(a) Water molecules (red and detail. An important characteristic of an aqueous solution of ions is that it
white) are in close proximity in will conduct electricity, provided the concentration of ions is not too low. An
liquid water. (b) Dissolved aqueous solution of ions conducts electricity because the ions move essen-
oxygen (red) and nitrogen tially independently of each other, each one carrying a certain quantity of
(blue) molecules are far apart, charge. (In a metallic conductor, such as copper or tungsten, electrons carry
separated by water molecules. the charge.) The manner in which ions conduct electric current is suggested
by Figure 5-2.
Whether or not an aqueous solution is a conductor of electricity depends
on the nature of the solute(s). Pure water contains so few ions that it does not
If a solute is completely conduct electric current. However, some solutes produce ions in solution,
ionized, then essentially all thereby making the solution an electrical conductor. Solutes that provide ions
the dissolved solute exists as
when dissolved in water are called electrolytes. Solutes that that do not pro-
ions. If a solute is partially
ionized, then only some (not
vide ions in water are called nonelectrolytes. All electrolytes provide ions in
all) of the solute molecules water but not all electrolytes are equal in their tendencies for providing ions.
have been converted into A strong electrolyte is a substance that is essentially completely ionized in
ions. aqueous solution. Stated another way, a strong electrolyte has a strong (or

FIGURE 5-2 Electricity e+

Conduction of electricity through a solution source
Two graphite rods called electrodes are placed in a
solution. The external source of electricity pulls e+
electrons from one rod and forces them onto the other, * +
creating a positive charge on one electrode and a
negative charge on the other (right). In the solution, *
positive ions (cations) are attracted to the negative +
electrode, the cathode; negative ions (anions) are +
*
attracted to the positive electrode, the anode. Thus, Anode Cathode
+
electric charge is carried through the solution by the
*
migration of ions. Other important aspects of electrical
+ *
conductivity are discussed in Chapter 20.
 5-1 The Nature of Aqueous Solutions 153

Solute

No Does it provide Yes

ions in water?

Nonelectrolyte Electrolyte

Is it completely
Yes ionized in water? No

FIGURE 5-3

*
Strong Weak A classification scheme for solutes

high) tendency for providing ions. A weak electrolyte is a substance that is

only partially ionized in aqueous solution. A weak electrolyte has a weak (or
small) tendency for providing ions. One scheme for classifying solutes is
summarized in Figure 5-3.
With the apparatus depicted in Figure 5-4, we can detect the presence of KEEP IN MIND
ions in an aqueous solution by measuring how well the solution conducts that the electrical conductiv-
electricity. We can make one of three possible observations: ity of a solution depends on
two factors: (1) the total con-
The lamp fails to light up (Fig. 5-4a). Conclusion: no ions are present (or if centration of the electrolyte,
some are present, their concentration is extremely low). The solution is and (2) the extent to which
either a solution of a nonelectrolyte or a very dilute solution of an elec- the electrolyte dissociates
trolyte. Methanol, CH 3OH, is an example of a solute that does not pro- into ions. For example, a
vide ions in water; methanol is a nonelectrolyte. The microscopic view in 0.001 M HCl(aq) solution
Figure 5-4(a) is for an aqueous solution of methanol, and in this view we will conduct electricity, but a
see that none of the CH 3OH molecules are ionized in water. 1 * 10-6 M HCl1aq2 solution
will not, even though every
The lamp lights up brightly (Fig. 5-4b). Conclusion: the concentration of HCl molecule dissociates
ions in solution is high. The solute is a strong electrolyte. Magnesium chlo- into H + and Cl - ions in both
ride, MgCl2, is an ionic compound that is completely ionized in water. solutions.
The microscopic view in Figure 5-4(b) shows that an aqueous solution of
MgCl2 consists of Mg 2+ and Cl- ions in the solvent.
The lamp lights up only dimly (Fig. 5-4c). Conclusion: ions are present in

solution of a weak electrolyte, such as acetic acid 1CH 3COOH2, or it

solution but the concentration of ions is low. The solution could be a

could be a dilute but not too dilute solution of a strong electrolyte.

The microscopic view in Figure 5-4(c) is for an aqueous solution of
CH 3COOH and it shows that, in water, only some of the CH 3COOH
molecules are ionized. An aqueous solution of CH 3COOH is only a weak
conductor of electricity.
The following generalization is helpful when deciding whether a particular
solute in an aqueous solution is most likely to be a nonelectrolyte, a strong
electrolyte, or a weak electrolyte.

Essentially all soluble ionic compounds and only a relatively few molecular
compounds are strong electrolytes.
Most molecular compounds are either nonelectrolytes or weak electrolytes.
154 Chapter 5 Introduction to Reactions in Aqueous Solutions

+
2*
+

+
2* +
+
2*
+
+
2*

(a) (b) (c)

FIGURE 5-4
Three types of electrolytes
KEEP IN MIND In (a), there are no ions present to speak of only molecules. Methanol (methyl
that the solvent molecules alcohol), CH3OH, is a nonelectrolyte in aqueous solutions. In (b), the solute is
are densely packed. In such present almost entirely as individual ions. MgCl2 is a strong electrolyte in aqueous
diagrams as Figure 5-4, we solutions. In (c), although most of the solute is present as molecules, a small fraction

CH3COOH molecules that ionize produce acetate ions CH3COO- and H+ ions,
will often show the solvent of the molecules ionize. CH3COOH is a weak electrolyte in aqueous solution. The
as a uniformly colored
background and depict only and the H+ ions attach themselves to water molecules to form hydronium ions,
the solute particles. H3O+.

Now let us consider how best to represent these three types of substances
in chemical equations. For water-soluble MgCl2, an ionic compound, we can

MgCl21aq2 " Mg2+1aq2 + 2 Cl-1aq2

write

dissociated into the separate ions. The best representation of MgCl21aq2, then,
This equation means that, in the presence of water, formula units of MgCl2 are

is Mg 2+1aq2 + 2 Cl -1aq2.
Hydrogen chloride, HCl, is an example of a molecular compound that is a

" H +1aq2 + Cl -1aq2

strong electrolyte. When HCl dissolves in water, the following reaction occurs:

The best representation of hydrochloric acid, HCl(aq), is H +1aq2 + Cl -1aq2.

The International HCl1aq2
Union of Pure and Applied
Chemistry (IUPAC) has
The hydrogen cation H + is an interesting and important species that has
recommended that the
H 3O +, ion be referred to as been the subject of intensive research. The ion H + a bare proton is a small
the oxonium ion. However, particle that interacts with the water molecules surrounding it. The simple
this recommendation has not hydrogen ion, H +, does not exist in aqueous solutions. Its actual form is as
yet been universally adopted hydronium ion, H 3O +, in which an H + ion is attached to an H 2O molecule. The
by chemists. hydronium ion, in turn, interacts with the water molecules surrounding it to
 5-1 The Nature of Aqueous Solutions 155

H H
O H O H O
H H
O H O H
O H H
H H
H H H O FIGURE 5-5

*
H The hydrated proton
H
The hydronium ion, H3O+, interacts
Hydronium ion A hydrated proton A hydrated proton with other water molecules through
H3O* H5O2* H9O4* electrostatic attractions.

form additional species, such as H 5O 2+, H 7O 3+, H 9O 4+ (shown in Figure 5-5)

proton is represented as H +1aq2, a shorthand notation. The interaction of the

and many others. These interactions are called hydration, and the hydrated

proton with a single water molecule is emphasized by using H 3O +1aq2. The

basis for these interactions will be discussed in Chapter 12 and employed
extensively in Chapter 16.
For a solution of a weak electrolyte, the reaction that produces ions does not KEEP IN MIND
go to completion. In such solutions, only a fraction of the solute molecules in
that there are different ways
solution are ionized. Equations for solutions of this type are written with dou-
to write the formulas for

H+1aq2 + CH3COO-1aq2
ble arrows, as shown below. acetic acid. The molecular
CH3COOH1aq2 formula, C2H 4O 2, makes no
distinction between the
The double arrows indicate that the process is reversible that is, while types of H atoms; HC2H 3O 2
some CH3COOH (acetic acid) molecules ionize, some H + and CH3COO- emphasizes that there is only
ions in solution recombine to form new CH3COOH molecules. However, one ionizable H atom; and
the relative proportions of ionized and nonionized (molecular) acid remain CH 3COOH and CH 3CO 2H

is best represented by CH3COOH (aq), not H+1aq2 + CH3COO -1aq2. If we

fixed. The predominant species is the molecule CH3COOH, and the solution emphasize that the ionizable
H atom is part of the carboxyl
could tag a particular CH3COO group and watch it over time, we would group. Recall: The carboxyl
group and carboxylic acids
sometimes see it as the ion CH3COO - , but most of the time it would be in a
were introduced in Chapter 3.
molecule, CH 3COOH.
For a nonelectrolyte, we simply write the molecular formula. Thus, for a
solution of methanol in water, we would write CH 3OH1aq2.
With this new information about the nature of aqueous solutions, we can
introduce a useful notation for solution concentrations. In a solution that is
0.0050 M MgCl2, we assume that the MgCl2 is completely dissociated into
ions. Because there are two Cl - ions for every Mg 2+ ion, the solution is

for the concentration of a species in solution the bracket symbol 3 4 . The

0.0050 M Mg 2+ but 0.0100 M Cl-. Better still, let us introduce a special symbol

statement 3Mg 2+4 = 0.0050 M means that the concentration of the

species within the brackets that is, Mg 2+ is 0.0050 mol>L. Thus,
in 0.0050 M MgCl2: 3Mg 2+4 = 0.0050 M; 3Cl -4 = 0.0100 M; 3MgCl24 = 0 M
Although we do not usually write expressions like 3MgCl24 = 0, it is done here
to emphasize that there is essentially no undissociated MgCl2 in the solution.*
Example 5-1 shows how to calculate the concentrations of ions in a strong
electrolyte solution.

*To say that a strong electrolyte is completely dissociated into individual ions in aqueous solu-
tion is a good approximation but somewhat of an oversimplification. Some of the cations and
anions in solution may become associated into units called ion pairs. Generally, though, at the
low solution concentrations we will be using, assuming complete dissociation will not seriously
affect our results.
156 Chapter 5 Introduction to Reactions in Aqueous Solutions

EXAMPLE 5-1 Calculating Ion Concentrations in a Solution of a Strong Electrolyte

What are the aluminum and sulfate ion concentrations in 0.0165 M Al21SO423?
Analyze

cal equation for the dissociation of Al21SO4231aq2, and then set up stoichiometric factors to relate Al3+ and
The solute is a strong electrolyte. Thus, it dissociates completely in water. First, we write a balanced chemi-

SO 42- to the molarity of Al21SO423.

The dissociation of Al21SO423 is represented by the equation below.

Solve

Al21SO4231s2 " 2 Al3+1aq2 + 3 SO 2-1aq2

H 2O
4

Al21SO423 produces 2 mol Al3+ and 3 mol SO 42-.

The stoichiometric factors, shown in blue in the following equations, are derived from the fact that 1 mol

0.0165 mol Al21SO423

3Al3+4 =
1 mol Al21SO423
2 mol Al3+ 0.0330 mol Al3+
* =
1L 1L

0.0165 mol Al21SO423

= 0.0330 M

3SO 42-4 =
1 mol Al21SO423
3 mol SO 42- 0.0495 mol SO 42-
* =
1L 1L
= 0.0495 M
Assess

ity. For example, in 0.0165 M MgCl2, we have 3Mg 2+4 = 1 * 0.0165 M and 3Cl -4 = 2 * 0.0165 M.
For a strong electrolyte, the concentrations of the ions will always be integer multiples of the electrolyte molar-

NaCl and 0.0512 M MgCl2. What is the molarity of Cl- that is, the total 3Cl-4 in seawater?
PRACTICE EXAMPLE A: The chief ions in seawater are Na+, Mg 2+ , and Cl -. Seawater is approximately 0.438 M

PRACTICE EXAMPLE B: A water treatment plant adds fluoride ion to the water to the extent of 1.5 mg F ->L.
(a) What is the molarity of fluoride ion in this water?
(b) If the fluoride ion in the water is supplied by calcium fluoride, what mass of calcium fluoride is present
in 1.00 * 106 L of this water?

5-1 CONCEPT ASSESSMENT

(1) Which solution is the best electrical conductor? (a) 0.50 M CH3COCH3;
(b) 0.50 M CH3CH2OH; (c) 1.00 M CH2OHCHOHCH2OH;
(d) 0.050 M CH3COOH; (e) 0.025 M RbNO3.
(2) Which solution has the highest total molarity of ions?

(d) 0.030 M HOCH2CH2OH; (e) 0.004 M Al21SO423?

(a) 0.008 M Ba1OH22; (b) 0.010 M KI; (c) 0.011 M CH3COOH;

5-2 Precipitation Reactions

Some metal salts, such as NaCl, are quite soluble in water, while others, such
as AgCl, are not very soluble at all. In fact, so little AgCl dissolves in water that
this compound is generally considered to be insoluble. Precipitation reactions
occur when certain cations and anions combine to produce an insoluble ionic
solid called a precipitate. One laboratory use of precipitation reactions is in
identifying the ions present in a solution, as shown in Figure 5-6. In industry,
precipitation reactions are used to manufacture numerous chemicals. In the
extraction of magnesium metal from seawater, for instance, the first step is to
 5-2 Precipitation Reactions 157

precipitate Mg 2+ as Mg1OH221s2. In this section, the objective is to represent

precipitation reactions by chemical equations and to apply some simple rules
for predicting precipitation reactions.

Net Ionic Equations

The reaction of silver nitrate and sodium iodide in an aqueous solution yields
sodium nitrate in solution and a pale yellow or cream-colored precipitate of
silver iodide, as shown in Figure 5-7. Applying the principles of equation writ-

AgNO31aq2 + NaI1aq2 ¡ AgI1s2 + NaNO31aq2

ing from Chapter 4, we can write
(5.1)
You might note a contradiction, however, between equation (5.1) and some-
thing we learned earlier in this chapter. In their aqueous solutions, the soluble
ionic compounds AgNO3, NaI, and NaNO 3 all strong electrolytes should

Ag +1aq2 + NO 3-1aq2 + Na+1aq2 + I -1aq2 ¡

be represented by their separate ions.

AgI1s2 + Na+1aq2 + NO 3- 1aq2

FIGURE 5-6
(5.2) Qualitative test for Cl *
in tap water

of a few drops of AgNO31aq2

We might say that equation (5.1) is the whole formula form of the equation,

Na+1aq2 and NO 3-1aq2 appear on both sides of the equation. These ions are not
The test involves the addition
whereas equation (5.2) is the ionic form. Notice also that in equation (5.2)
to tap water. The formation of
reactants; they go through the reaction unchanged. We call them spectator ions. a precipitate of AgCl(s)

Ag +1aq2 + I -1aq2 ¡ AgI1s2

If we eliminate the spectator ions, all that remains is the net ionic equation: confirms the presence of Cl-.
(5.3)
A net ionic equation is an equation that includes only the actual partici- KEEP IN MIND
pants in a reaction, with each participant denoted by the symbol or formula that although the insoluble

Ag +1aq2, and whole formulas are written for insoluble solids, such as AgI(s).
that best represents it. Symbols are written for individual ions, such as solid consists of ions, we
don t represent ionic charges

we write AgI(s), not Ag +I -1s2.

in the whole formula. That is,
Because net ionic equations include electrically charged species ions a net
ionic equation must be balanced both for the numbers of atoms of all types
and for electric charge. The same net electric charge must appear on both sides
of the equation. Throughout the remainder of this chapter, we will represent
most chemical reactions in aqueous solution by net ionic equations.

Predicting Precipitation Reactions

Suppose we are asked whether precipitation occurs when the following aque-

AgNO31aq2 + KBr1aq2 ¡ ?
ous solutions are mixed.
(5.4)

FIGURE 5-7
A precipitate of silver iodide
When an aqueous solution of AgNO3
(a) is added to one of NaI (b), insoluble
pale yellow or cream-colored AgI(s)
precipitates from solution (c).
(a) (b) (c)
158 Chapter 5 Introduction to Reactions in Aqueous Solutions

Ag +1aq2 + NO 3-1aq2 + K +1aq2 + Br -1aq2 ¡ ?

A good way to begin is to rewrite expression (5.4) in the ionic form.
(5.5)
There are only two possibilities. Either some cation anion combination leads
to an insoluble solid a precipitate or no such combination is possible, and
there is no reaction at all.
To predict what will happen without doing experiments, we need some
information about which sorts of ionic compounds are water soluble and
which are water insoluble. We expect the insoluble ones to form when the
appropriate ions are mixed in solution. We don t have all-encompassing rules
for predicting solubilities, but a few guidelines work for the majority of com-
mon ionic solutes. A concise form of these guidelines is presented in Table 5.1.

In principle, all ionic

*

TABLE 5.1 Solubility Guidelines for Common Ionic Solids

compounds dissolve in
water to some extent, though Follow the lower-numbered guideline when two guidelines are in conflict. This
this may be very slight. leads to the correct prediction in most cases.
For practical purposes, we 1. Salts of group 1 cations (with some exceptions for Li + ) and the NH 4+ cation are
consider a compound to be soluble.
insoluble if the maximum 2. Nitrates, acetates, and perchlorates are soluble.
amount that can dissolve is 3. Salts of silver, lead, and mercury(I) are insoluble.
less than about 0.01 mol>L. 4. Chlorides, bromides, and iodides are soluble.
5. Carbonates, phosphates, sulfides, oxides, and hydroxides are insoluble
(sulfides of group 2 cations and hydroxides of Ca2+, Sr 2+, and Ba2+ are
slightly soluble).
6. Sulfates are soluble except for those of calcium, strontium, and barium.

KEEP IN MIND The guidelines from Table 5.1 are applied in the order listed, with the lower-
numbered guideline taking precedence in cases of a conflict. According to

dence over rule 4) and should precipitate, whereas KNO31s2 is soluble

that when two ionic
compounds form a solid
these guidelines, AgBr(s) is insoluble in water (because rule 3 takes prece-
precipitate, they do so by

Ag +1aq2 + NO 3-1aq2 + K +1aq2 + Br -1aq2 ¡ AgBr1s2 + K +1aq2 + NO 3-1aq2

exchanging ions. In the (because of rule 1). Written as an ionic equation, expression (5.5) becomes
formation of AgBr from KBr
and AgNO 3, the following

Ag +1aq2 + Br -1aq2 ¡ AgBr1s2

exchange takes place. For the net ionic equation, we have
K* * Br+ (5.6)
The three predictions concerning precipitation reactions made in Example 5-2
Ag* * NO3+ are verified in Figure 5-8.
*

FIGURE 5-8

(a) When NaOH(aq) is added to MgCl21aq2, a white

Verifying the predictions made in Example 5-2

precipitate of Mg1OH221s2 forms. (b) When colorless

BaS(aq) is added to blue CuSO41aq2, a dark

BaSO41s2 and black CuS(s); a slight excess of CuSO4

precipitate forms. The precipitate is a mixture of white

colorless 1NH422SO41aq2 is added to colorless

remains in solution. (c) No reaction occurs when

ZnCl21aq2.
(a) (b) (c)
 5-2 Precipitation Reactions 159

EXAMPLE 5-2 Using Solubility Guidelines to Predict Precipitation Reactions

(a) NaOH1aq2 + MgCl21aq2 ¡ ?

Predict whether a reaction will occur in each of the following cases. If so, write a net ionic equation for the reaction.

(b) BaS1aq2 + CuSO41aq2 ¡ ?

(c) 1NH 422SO41aq2 + ZnCl21aq2 ¡ ?
Analyze
All the compounds shown in (a), (b), and (c) are soluble and they provide ions in solution. By using the solubil-
ity guidelines in Table 5.1, determine whether the positive ions from one compound combine with the negative
ions of the other to form soluble or insoluble compounds. If only soluble compounds are formed, then all ions
remain in solution (no reaction). If an insoluble compound is formed, then the insoluble compound precipitates
from the solution. The net ionic equation for the precipitation reaction is obtained by eliminating the spectator
ions from the full ionic equation.
Solve
For each of (a), (b) and (c), apply the strategy described above.
(a) In aqueous solution, we get Na+ and OH - from NaOH and Mg 2+ and Cl- from MgCl2. The combina-
tion of Na + and Cl - gives NaCl, a soluble compound; thus, the Na+ and Cl - ions remain in solution.
However, the Mg 2+ and OH - ions combine to produce Mg1OH22, an insoluble compound. The full,
ionic equation is

2 Na+1aq2 + 2 OH -1aq2 + Mg 2+1aq2 + 2 Cl -1aq2 ¡

Mg1OH221s2 + 2 Na+1aq2 + 2 Cl -1aq2

2 OH -1aq2 + Mg 2+1aq2 ¡ Mg1OH221s2

With the elimination of spectator ions, we obtain

(b) In aqueous solution, we get Ba2+ and S 2- from BaS and Cu2+ and SO 42- from CuSO4. The Ba2+ and
SO 42- ions combine to form BaSO4, an insoluble compound, and the Cu2+ and S 2- ions combine to form

Ba2+1aq2 + S 2-1aq2 + Cu2+1aq2 + SO 42-1aq2 ¡ BaSO41s2 + CuS1s2

CuS, also an insoluble compound. The full ionic equation is

The equation above is also the net ionic equation because there are no spectator ions.
(c) We get NH 4+, SO 42-, Zn2+, and Cl - ions in solution. Because all possible combinations of positive and
negative ions lead to water soluble compounds, all of the ions remain
in solution. No reaction occurs. Mg(OH)2 is
Na* * OH+ insoluble.
Assess
Problems of this type can also be solved by using a diagrammatic approach
which is illustrated for part (a). Mg2* * 2 Cl+ NaCl is
As you gain experience, you should be able to go directly to a net ionic soluble.
equation without first having to write an ionic equation that includes spectator ions.
PRACTICE EXAMPLE A: Indicate whether a precipitate forms by completing each equation as a net ionic

(a) AlCl31aq2 + KOH1aq2 ¡ ?

equation. If no reaction occurs, so state.

(b) K 2SO41aq2 + FeBr31aq2 ¡ ?

(c) CaI 21aq2 + Pb1NO3221aq2 ¡ ?

PRACTICE EXAMPLE B: Indicate through a net ionic equation whether a precipitate forms when the following
compounds in aqueous solution are mixed. If no reaction occurs, so state.
(a) sodium phosphate + aluminum chloride ¡ ?
(b) aluminum sulfate + barium chloride ¡ ?
(c) ammonium carbonate + lead nitrate ¡ ?
160 Chapter 5 Introduction to Reactions in Aqueous Solutions

5-2 CONCEPT ASSESSMENT

Apply the solubility guidelines in Table 5.1 to predict whether each of the

guidelines inconclusive? (a) Al21SO423; (b) Cr1OH23; (c) K3PO4; (d) Li2CO3;
following solids is water soluble or insoluble. For which are the solubility

(e) ZnS; (f ) Mg1MnO422; (g) AgClO4; (h) CaSO4; (i) PbO.

5-1 ARE YOU WONDERING...

Whether an insoluble ionic compound, such as AgCl,
is a strong electrolyte or a weak electrolyte?
Silver chloride, AgCl, is an ionic compound. When AgCl dissolves in water, it is
100% dissociated into Ag + and Cl - ions; there are no AgCl ion pairs. If we focus
only on the degree of dissociation, then AgCl, like HCl, is a strong electrolyte.
At one time, a strong electrolyte was defined in more practical terms as a
substance that when dissolved in water, gives a solution that is a good conductor
of electricity. Because AgCl has very low solubility in water, approximately
1 * 10-5 moles per liter, a solution of AgCl is not a good conductor of electricity.
Today, most chemists would argue that AgCl is a strong electrolyte (because it is
100% dissociated in aqueous solution) but some may argue that it is a weak elec-
trolyte (because an aqueous solution of AgCl is not a good conductor of electricity).
Does it matter that chemists may not totally agree on whether AgCl should be
called a strong electrolyte or a weak electrolyte? Not at all, because all chemists
agree on the following facts: (1) AgCl is essentially 100% dissociated in water;
(2) only a small amount of AgCl can be dissolved in water; and (3) an aqueous
solution of AgCl is not a good conductor of electricity.

5-3 Acid Base Reactions

Ideas about acids and bases (or alkalis) date back to ancient times. The word
acid is derived from the Latin acidus (sour). Alkali (base) comes from the Arabic
al-qali, referring to the ashes of certain plants from which alkaline substances
can be extracted. The acid base concept is a major theme in the history of
chemistry. In this section, we emphasize the view proposed by Svante
Arrhenius in 1884 but also introduce a more modern theory proposed in 1923
by Thomas Lowry and by Johannes Brønsted.

Acids
From a practical standpoint, acids can be identified by their sour taste, their
ability to react with a variety of metals and carbonate minerals, and the effect
they have on the colors of substances called acid base indicators. Methyl red is
an acid base indicator that appears red in acidic environments and yellow

can be defined as a substance that provides hydrogen ions 1H +2 in aqueous

otherwise (see Figure 5-9). From a chemist s point of view, however, an acid

that H +1aq2 actually

KEEP IN MIND solution. This definition was first proposed by Svante Arrhenius in 1884.
Different acids exhibit different tendencies for producing H + ions in aque-
represents a hydrated proton, ous solution. Strong acids have a strong tendency for producing H + ions.

into H +1aq2 and accompanying anions when in aqueous solution. Hydrogen

that is, a proton attached Strong acids are molecular compounds that are almost completely ionized
to one H 2O molecule, as in

dissolves in water, complete ionization into H +1aq2 and Cl -1aq2 occurs:

H 3O +, or to several H 2O
molecules, as in H 9O 4 +.
chloride, HCl, and nitric acid, HNO3, are examples of strong acids. When HCl

HCl1aq2 ¡ H +1aq2 + Cl -1aq2 (5.7)

 5-3 Acid Base Reactions 161

FIGURE 5-9

*
An acid, a base, and an acid base indicator
The acidic nature of lemon juice is shown by the red
color of the acid base indicator methyl red. The basic
nature of soap is indicated by the change in color of the
indicator from red to yellow.

When HNO3 dissolves in water, complete ionization into H +1aq2 and

NO 3-1aq2 occurs. There are so few common strong acids that they make only a
TABLE 5.2 Common
Strong Acids and
short list. The list of common strong acids is given in Table 5.2. It is imperative Strong Bases
that you memorize this list.
Weak acids are molecular compounds that have a weak tendency for pro- Acids Bases
ducing H + ions; weak acids are incompletely ionized in aqueous solution. The
vast majority of acids are weak acids. The ionization of a weak acid is best HCl LiOH
described in terms of a reversible reaction that does not go to completion. As HBr NaOH
HI KOH

H+1aq2 + CH3COO-1aq2
described on page 155, the ionization reaction for acetic acid, CH3COOH, is
HClO4 RbOH
CH3COOH1aq2 (5.8) HNO3 CsOH
Equation (5.8) has the following interpretation: in aqueous solution, only H 2SO 4a Ca1OH22
some of the CH3COOH molecules are converted into H + and CH3COO - ions. Sr1OH22
The fraction of molecules that ionize can be calculated, but the calculation is Ba1OH22
not simple. We will defer such calculations until Chapter 16. aH
2SO4 ionizes in two
Equations (5.7) and (5.8) are based on the Arrhenius theory of acids and distinct steps. It is a strong
bases, and these equations might lead you to think that acids simply fall acid only in its first ionization
apart into H + ions and the accompanying anions when they are dissolved in step (see Section 16-6).
water. However, plenty of experimental evidence proves that this is not the
case. In 1923, Johannes Brønsted in Denmark and Thomas Lowry in Great
Britain independently proposed that the key process responsible for the KEEP IN MIND
properties of acids (and bases) was the transfer of an H + ion (a proton) from
that a hydrogen atom
one substance to another. For example, when acids dissolve in water, H + consists of one proton and
ions are transferred from acid molecules to water molecules, as shown below one electron. Therefore, a

HCl1aq2 + H 2O1l2 ¡ H 3O +1aq2 + Cl -1aq2

for HCl and CH3COOH. hydrogen ion, H +, is simply a

H3O 1aq2 + CH3COO 1aq2

proton.
(5.9)
+ -
CH3COOH1aq2 + H2O1l2 (5.10)
In equations (5.9) and (5.10), the acid molecules are acting as proton donors
and the water molecules are acting as proton acceptors. According to the
Brønsted-Lowry theory, an acid is a proton donor.
It is partly a matter of preference whether we include water as a reactant in
the equation for the reaction that occurs when an acid is dissolved in water.
Some chemists prefer to write the reaction without water as a reactant, as we
did in equations (5.7) and (5.8), to eliminate the clutter of extra water mole-
cules. If that is also your preference, then you must remember that the H + ion is
not a free proton in solution but rather is firmly bound to a water molecule and
exists as an H 3O + ion. The H 3O + ion is even further hydrated (see Figure 5-5).
Many chemists prefer to include H 2O as a reactant, as we did in equations (5.9)
and (5.10), to emphasize that the reactions actually involve the transfer of pro-
tons from acid molecules to water molecules.
162 Chapter 5 Introduction to Reactions in Aqueous Solutions

Bases
From a practical standpoint, we can identify bases through their bitter taste,
slippery feel, and effect on the colors of acid base indicators (Fig. 5-9). The

1OH -2 in aqueous solution. Consider a soluble ionic hydroxide, such as

Arrhenius definition of a base is a substance that produces hydroxide ions

NaOH. In the solid state, this compound consists of Na + and OH - ions. When
the solid dissolves in water, the ions dissociate.

The equation above indicates that NaOH(aq) is best represented as Na+1aq2

NaOH(aq) ¡ Na+(aq) + OH -(aq)

plus OH -(aq).
A base that dissociates completely, or very nearly so, in aqueous solution is a
strong base. As is true of strong acids, the number of common strong bases is
small (see Table 5.2). They are primarily the hydroxides of group 1 and some
group 2 metals. Memorize the list.
Certain substances produce OH - ions by reacting with water, not just by

NH 31aq2 + H 2O1l2 NH 4 + 1aq2 + OH -1aq2

dissolving in it. Such substances, for example, ammonia, are also bases.
(5.11)
NH 3 is a weak electrolyte; its reaction with water does not go to completion. A
that NH 4 1aq2 is formed by
KEEP IN MIND
+ base that is incompletely ionized in aqueous solution is a weak base. Most
the transfer of a proton from
basic substances are weak bases.
an H 2O to a NH 3 molecule, We can also examine equation (5.11) in terms of the Brønsted-Lowry theory,
and NH 4 + interacts with which focuses on the transfer of protons from one substance to another.
water in much the same way According to this theory, a base is a proton acceptor. In equation (5.11), NH 3
as the hydronium ion does. behaves as a proton acceptor (a Brønsted-Lowry base) and H 2O behaves as a
A ball-and-stick model of the proton donor (a Brønsted-Lowry acid).
ammonium ion is shown
below.
Acidic and Basic Solutions
We have seen that when dissolved in water, an acid produces H + ions and a
base produces OH - ions. However, experiment shows small numbers of H +

reaction occurs to a limited extent, hence the use of a double arrow 1 2

and OH - ions are present even in pure water. In pure water, the following

rather than a single arrow 1¡ 2.

H +1aq2 + OH -1aq2
Ammonium ion

Careful measurements show that 3H +4water = 3OH -4water = 1.0 * 10-7 M

H 2O1l2

the values given for 3H +4 and 3OH -4 are for pure water only.) Because an acid
at 25 °C. (The subscripts on the square brackets are there to emphasize that

have 3H +4 7 1.0 * 10-7 M. Such a solution is said to be acidic. An acidic solution

produces H + ions in solution, we expect that a solution of acid at 25 °C will

OH - ions, and so a solution of base will have 3OH -4 7 1.0 * 10-7 M at 25 °C.
has a greater concentration of H + ions than does pure water. A base produces

Such a solution is said to be basic. These ideas are summarized below.

An acidic solution has 3H+4 7 3H+4water.

A basic solution has 3OH-4 7 3OH-4water.

The statements above can be expressed another way. An acidic solution has
an excess of H + ions (compared with pure water), and a basic solution has an
excess of OH - ions. We will use these ideas in Section 5-5 and encounter them
again in Chapter 16.
 5-3 Acid Base Reactions 163

Neutralization
Perhaps the most significant property of acids and bases is the ability of each
to cancel or neutralize the properties of the other. In a neutralization reaction,
an acid and a base react to form water and an aqueous solution of an ionic
compound called a salt. Thus, in molecular form,

1acid2 1base2 1salt2 + 1water2

HCl1aq2 + NaOH1aq2 ¡ NaCl1aq2 + H 2O1l2
+ ¡

Switching to the ionic form we write,

H +(aq) + Cl -(aq) + Na +(aq) + OH -(aq) ¡ Na+(aq) + Cl -(aq) + H 2O(l)

¯ ¯ ¯ ¯
(acid) (base) salt water

When the spectator ions are eliminated, the net ionic equation shows the
essential nature of the neutralization of a strong acid by a strong base: H + ions
from the acid and OH - ions from the base combine to form water.

H +1aq2 + OH -1aq2 ¡ H 2O1l2

In a neutralization involving the weak base NH 31aq2, we can think of H + The formula of NH 31aq2

*
from an acid combining directly with NH 3 molecules to form NH 4 +. The neu- is sometimes written as
tralization can be represented by an ionic equation, for example, NH 4OH (ammonium

H +1aq2 + Cl -1aq2 + NH 31aq2 ¡ NH 4 +1aq2 + Cl -1aq2

hydroxide) and its ionization
represented as
¯ ¯ ¯

NH 4+1aq2 + OH -1aq2
(acid) (base) (salt) NH 4OH1aq2

or by a net ionic equation

H +1aq2 + NH 31aq2 ¡ NH 4 +1aq2

There is no hard evidence for
the existence of NH 4OH,
however, that is, in the sense
All the neutralization reactions given above involve a strong acid or a strong of a discrete substance

reagent is used up. Thus, we use a single arrow 1¡ 2 rather than a double
base and all of them go essentially to completion, that is, until the limiting comprising NH 4 + and OH -

formula NH 31aq2.
arrow 1 2 in the equations for these reactions.
ions. We will use only the

Recognizing Acids and Bases

Acids contain ionizable hydrogen atoms, which are generally identified by the
way in which the formula of an acid is written. Ionizable H atoms are sepa-
rated from other H atoms in the formula either by writing them first in the
molecular formula or by indicating where they are found in the molecule.
Thus, there are two ways that we can show that one H atom in the acetic acid
molecule is ionizable and the other three H atoms are not.

HC2H 3O2 or CH 3COOH

¯
acetic acid

In contrast to acetic acid, methane has four H atoms, but they are not ioniz-
able. CH 4 is neither an acid nor a base.
A substance whose formula indicates a combination of OH - ions with
cations is generally a strong base (for example, NaOH). To identify a weak
base, we usually need a chemical equation for the ionization reaction, as in
equation (5.11). The main weak base we will work with at present is NH 3.
Note that ethanol, CH3CH2OH, is not a base. The OH group is not present as
OH -, both in pure ethanol and in its aqueous solutions.
164 Chapter 5 Introduction to Reactions in Aqueous Solutions

More Acid Base Reactions

Mg1OH22 is a base because it contains OH -, but this compound is quite insol-
uble in water. Its finely divided solid particles form a suspension in water that

Mg1OH221s2 does dissolve very slightly, producing some OH - in solution. If

is the familiar milk of magnesia, used as an antacid. In this suspension,

neutralization occurs. More Mg1OH221s2 dissolves to produce more OH - in

an acid is added, H + from the acid combines with this OH - to form water

solution, which is neutralized by more H +, and so on. In this way, the neu-

Mg1OH221s2. The net ionic equation for the reaction of Mg1OH221s2 with a
tralization reaction results in the dissolving of otherwise insoluble

Mg1OH221s2 + 2 H +1aq2 ¡ Mg 2+1aq2 + 2 H 2O1l2

strong acid is

Mg1OH221s2 also reacts with a weak acid, such as acetic acid. In the net
(5.12)

ionic equation, acetic acid is written in its molecular form. But remember that
some H + and CH 3COO - ions are always present in an acetic acid solution.
The H + ions react with OH - ions, as in reaction (5.12), followed by further ion-
ization of CH 3COOH, more neutralization, and so on. If enough acetic acid is
present, the Mg1OH22 will dissolve completely. The equation for the reaction

Mg1OH221s2 + 2 CH3COOH1aq2 ¡ Mg2+1aq2 + 2 CH3COO-1aq2 + 2 H2O1l2

is given below.

(5.13)
Calcium carbonate, which is present in limestone and marble, is another
water-insoluble solid that is soluble in strong and weak acids. Here the solid
produces a low concentration of CO3 2- ions, which combine with H + to form
the weak acid H 2CO 3. This causes more of the solid to dissolve, and so on.

and CO21g2. The net ionic equation for the reaction of CaCO 3 with an acid is
Carbonic acid, H 2CO3, is a very unstable substance that decomposes into H 2O
FIGURE 5-10

CaCO31s2 + 2 H +1aq2 ¡ Ca2+1aq2 + H 2O1l2 + CO21g2

Damage caused by given below.
acid rain

Thus, a gas is given off when CaCO31s2 reacts with an acid and dissolves.
This marble statue has been (5.14)
eroded by acid rain. Marble
consists primarily of CaCO3. The reaction represented by equation (5.14) is responsible for the erosion of

(5.14) also shows that CaCO31s2 has the ability to neutralize acids. Not sur-
Acids react with and dissolve marble statues by acid rain, such as the one shown in Figure 5-10. Equation
marble through the reaction
described in equation (5.14).
prisingly, calcium carbonate, like magnesium hydroxide, is used as an
antacid.
The Arrhenius definition recognizes only OH - as a base, but when we
reconsider acids and bases in more detail in Chapter 16, we will see that mod-
ern theories identify CO3 2- and many other anions, including OH -, as bases.
Table 5.3 lists several common anions and one cation that produce gases in
acid base reactions.

TABLE 5.3 Some Common Gas-Forming Reactions

HSO3 - + H + ¡ SO21g2 + H 2O1l2

Ion Reaction

SO 3 2- + 2 H + ¡ SO21g2 + H 2O1l2
HSO 3 -

HCO 3- + H + ¡ CO21g2 + H 2O1l2

SO3 2-

CO 3 2- + 2 H + ¡ CO21g2 + H 2O1l2
HCO3 -
CO3 2-

NH 4 + + OH - ¡ NH 31g2 + H 2O1l2
S 2- S 2- + 2 H + ¡ H 2S1g2
NH 4 +
 5-4 Oxidation Reduction Reactions: Some General Principles 165

EXAMPLE 5-3 Writing Equations for Acid Base Reactions

Write a net ionic equation to represent the reaction of (a) aqueous strontium hydroxide with nitric acid;
(b) solid aluminum hydroxide with hydrochloric acid.
Analyze
The reactions are neutralization reactions, which means they are of the general form acid + base : salt + water.
We can start with the whole formula equation, switch to the ionic equation, and then delete the spectator ions
to arrive at the net ionic equation.

(a) 2 HNO31aq2 + Sr1OH221aq2 ¡ Sr1NO3221aq2 + 2 H 2O1l2

Solve

2 H +1aq2 + 2 NO3 -1aq2 + Sr 2+1aq2 + 2 OH -1aq2 ¡ Sr 2+1aq2 + 2 NO 3 -1aq2 + 2 H 2O1l2

Ionic form:

2 H +1aq2 + 2 OH -1aq2 ¡ 2 H 2O1l2

Net ionic equation: Delete the spectator ions (Sr 2+ and NO3 - ).

H +1aq2 + OH -1aq2 ¡ H 2O1l2

or, more simply,

(b) Al1OH231s2 + 3 HCl1aq2 ¡ AlCl31aq2 + 3 H 2O1l2

Al1OH231s2 + 3 H +1aq2 + 3 Cl -1aq2 ¡ Al3+1aq2 + 3 Cl -1aq2 + 3 H 2O1l2

Ionic form:

Net ionic equation: Delete the spectator ion 1Cl-2.

Al1OH231s2 + 3 H +1aq2 ¡ Al3+1aq2 + 3 H 2O1l2

In part (a), the net ionic equation is H +1aq2 + OH -1aq2 : H 2O1l2, as is always the case when the neutraliza-
Assess

tion reaction involves a soluble strong acid and a soluble strong base. In part (b), the base was not soluble;
thus, the net ionic equation includes a solid.

PRACTICE EXAMPLE A: Write a net ionic equation to represent the reaction of aqueous ammonia with
propionic acid, CH3CH2COOH. Assume that the neutralization reaction goes to completion. What is the
formula and name of the salt that results from this neutralization?

PRACTICE EXAMPLE B: Calcium carbonate is a major constituent of the hard water deposits found in teakettles
and automatic coffeemakers. Vinegar, which is essentially a dilute aqueous solution of acetic acid, is
commonly used to remove such deposits. Write a net ionic equation for the reaction that occurs. Assume that
the neutralization reaction goes to completion.

5-3 CONCEPT ASSESSMENT

H2O1l2, HCl1aq2, and H2SO41aq2. You are asked to prepare four solutions, each
You are given the four solids, K2CO3, CaO, ZnSO4, and BaCO3, and three solvents,

containing one of the four cations, that is, one with K+1aq2, one with Ca2+1aq2,
and so on. Using water as your first choice, what solvent would you use to prepare
each solution? Explain your choices.

5-4 Oxidation Reduction Reactions:

Some General Principles An ore is a mineral from
*

which a metal can be

Practical applications of oxidation reduction reactions can be traced back thou- extracted. Many metal ores
sands of years to the period in human culture when metal tools were first made.

such as cuprite 1Cu 2O2 or hematite 1Fe2O32, in the presence of carbon. Since
are oxides and the metals are
The metal needed to make tools was obtained by heating copper or iron ores, obtained from their oxides by
the removal of oxygen.
166 Chapter 5 Introduction to Reactions in Aqueous Solutions

that time, iron has become the most widely used of all metals and it is produced
in essentially the same way: by heating Fe2O3 in the presence of carbon in a

Fe2O31s2 + 3 CO1g2 " 2 Fe1l2 + 3 CO 1g2

blast furnace. A simplified chemical equation for the reaction is given below.
¢
In a blast furnace, carbon 2 (5.15)

to produce CO21g2 and the free element iron. A commonly used term to
from the coke is converted to
CO, which then reacts with In this reaction, we can think of the CO1g2 as taking O atoms away from Fe2O3
Fe2O3.
describe a reaction in which a substance gains O atoms is oxidation, and a reac-

is oxidized and Fe2O 31s2 is reduced. Oxidation and reduction must always
tion in which a substance loses O atoms is reduction. In reaction (5.15), CO1g2

Because it is easier to say, occur together, and such a reaction is called an oxidation reduction, or redox,
the term redox is often used reaction. The oxygen in Fe2O 3 can also be removed by igniting a finely
instead of oxidation reduction. divided mixture of Fe2O3 and Al. The reaction produces a spectacular display,
shown in Figure 5-11, and releases a tremendous amount of heat, which causes
the iron to melt. Mixtures of finely divided Fe2O3 and Al are used by railway
workers to produce liquid iron for welding together iron railway tracks.
Definitions of oxidation and reduction based solely on the transfer of
O atoms are too restrictive. By using broader definitions, many reactions in
aqueous solution can be described as oxidation reduction reactions, even
when no oxygen is involved.

Oxidation State Changes

Suppose we rewrite equation (5.15) and indicate the oxidation states (O.S.) of the
elements on both sides of the equation by using the rules listed on page 85.
FIGURE 5-11
Thermite reaction *3 +2 *2 +2 0 *4+2
Iron atoms of iron(III) oxide
give up O atoms to Al atoms, Fe2O3 * 3 CO 2 Fe * 3 CO2

Fe2O31s2 + 2 Al1s2 ¡
producing Al2O3. The O.S. of oxygen is - 2 everywhere it appears in this equation. That of

Al2O31s2 + 2 Fe1l2
iron (shown in red) changes. It decreases from + 3 in Fe2O3 to 0 in the free ele-
ment, Fe. The O.S. of carbon (shown in blue) also changes. It increases from + 2
in CO to + 4 in CO 2. In terms of oxidation state changes, in an oxidation
process, the O.S. of some element increases; in a reduction process, the O.S. of
some element decreases.
Even though we assess oxidation state changes by element, oxidation and
reduction involve the entire species in which the element is found. Thus, for
the reaction above, the whole compound Fe2O3 is reduced, not just the
Fe atoms; and CO is oxidized, not just the C atom.

EXAMPLE 5-4 Identifying Oxidation Reduction Reactions

(a) MnO21s2 + 4 H +1aq2 + 2 Cl -1aq2 ¡ Mn2+1aq2 + 2 H 2O1l2 + Cl21g2

Indicate whether each of the following is an oxidation reduction reaction.

(b) H 2PO4 -1aq2 + OH -1aq2 ¡ HPO4 2-1aq2 + H 2O1l2

Analyze
In each case, indicate the oxidation states of the elements on both sides of the equation, and look for changes.
Solve
(a) The O.S. of Mn decreases from + 4 in MnO2 to + 2 in Mn2+. MnO2 is reduced to Mn2+. The O.S. of
O remains at - 2 throughout the reaction, and that of H, at + 1. The O.S. of Cl increases from - 1 in Cl- to
0 in Cl2. Cl- is oxidized to Cl2. The reaction is an oxidation reduction reaction.
(b) The O.S. of H is + 1 on both sides of the equation. Oxygen remains at O.S. - 2 throughout. The O.S. of
phosphorus is + 5 in H 2PO 4 - and also + 5 in HPO 4 2-. There are no changes in O.S. This is not an
oxidation reduction reaction. (It is, in fact, an acid base reaction.)
 5-4 Oxidation Reduction Reactions: Some General Principles 167

Assess
Because many redox reactions involve H +, OH -, or insoluble ionic compounds, it is easy to confuse a redox
reaction with an acid base or a precipitation reaction. It is important that you remember the defining features

uble precipitate, acid base reactions involve proton 1H +2 transfer, and redox reactions involve electron transfer
of each type of reaction. Precipitation reactions involve the combination of ions in solution to produce an insol-

and changes in oxidation states.

(a) 1NH 422SO41aq2 + Ba1NO 3221aq2 ¡ BaSO41s2 + 2 NH 4NO31aq2

PRACTICE EXAMPLE A: Identify whether each of the following is an oxidation reduction reaction.

(b) 2 Pb1NO3221s2 ¡ 2 PbO1s2 + 4 NO21g2 + O 21g2

5 VO 2+1aq2 + MnO4 -1aq2 + H 2O1l2 ¡ 5 VO 2 +1aq2 + Mn2+1aq2 + 2 H +1aq2

PRACTICE EXAMPLE B: Identify the species that is oxidized and the species that is reduced in the reaction below.

Oxidation and Reduction Half-Reactions

The reaction illustrated in Figure 5-12 is an oxidation reduction reaction. The

Zn1s2 + Cu2+1aq2 ¡ Zn2+1aq2 + Cu1s2

chemical equation for the reaction is given below.

We can show that the reaction is an oxidation reduction reaction by evaluat-

ing changes in oxidation state, but there is another especially useful way to
establish this. Think of the reaction as involving two half-reactions occurring
at the same time an oxidation and a reduction. The overall reaction is the

(a) (b) (c)

Zn Cu FIGURE 5-12
An oxidation reduction reaction

immersion of the Zn rod in the CuSO41aq2 for several hours, the blue color
2e+ (a) A zinc rod above an aqueous solution of copper(II) sulfate. (b) Following
Cu2* of Cu2+1aq2 disappears and a deposit of copper forms on the rod. In the
2e+ microscopic view on the left, the gray spheres represent Zn atoms and the
Zn2* red spheres represent Cu atoms. In the reaction, Zn atoms lose electrons to
the metal surface and enter the solution as Zn2+ ions. Cu2+ ions from the
solution pick up electrons and deposit on the metal surface as atoms of
Zn2* solid copper. (c) The pitted zinc rod (providing evidence that zinc was
consumed in a chemical reaction) and the collected copper metal.
168 Chapter 5 Introduction to Reactions in Aqueous Solutions

sum of the two half-reactions. We can represent the half-reactions by half-

Zn1s2 ¡ Zn2+ 1aq2 + 2 e -

equations and the overall reaction by an overall equation.

Cu2+1aq2 + 2 e - ¡ Cu1s2
Oxidation: (5.16)

Zn1s2 + Cu 1aq2 ¡ Zn 1aq2 + Cu1s2

Reduction: (5.17)
2+ 2+
Overall: (5.18)
In half-reaction (5.16), Zn is oxidized its oxidation state increases from 0 to
+ 2. This change corresponds to a loss of two electrons by each zinc atom. In half-
reaction (5.17), Cu2+ is reduced its oxidation state decreases from + 2 to 0. This
change corresponds to the gain of two electrons by each Cu2+ ion. To summarize,
Oxidation is a process in which the O.S. of some element increases as elec-
trons are lost. Electrons appear on the right side of a half-equation.
Reduction is a process in which the O.S. of some element decreases as
electrons are gained. Electrons appear on the left side of a half-equation.
Oxidation and reduction half-reactions must always occur together, and
the total number of electrons associated with the oxidation must equal the
total number associated with the reduction.
Redox reactions are similar to acid base reactions in that both types of reac-
tions involve the transfer of small, fundamental particles; protons are trans-
ferred in acid base reactions and electrons are transferred in redox reactions.

atoms and protons 1H +2 are shown explicitly in the balanced chemical equa-
However, acid-base reactions are easily identified because the hydrogen

tion. Redox reactions are much more difficult to identify because the electrons
are hidden. When we write out the half-equations for the oxidation and
reduction processes, the electrons are shown explicitly and the key feature of a
redox reaction, electron transfer, is emphasized.
Figure 5-13 and Example 5-5 suggest some fundamental questions about

Why does Fe react with HCl1aq2, displacing H 21g2, whereas Cu does not?
oxidation reduction. For example,

Why does Fe form Fe 2+ and not Fe 3+ in this reaction?

EXAMPLE 5-5 Representing an Oxidation Reduction Reaction Through

Half-Equations and an Overall Equation

of iron with hydrochloric acid solution to produce H 21g2 and Fe 2+ . The reaction is shown in Figure 5-13.
Write equations for the oxidation and reduction processes that occur and the overall equation for the reaction

The reactants are Fe1s2 and HCl1aq2, and the products are H 21g2 and FeCl21aq2, a soluble ionic compound. In
Analyze

the reaction, the oxidation state of iron changes from 0 in Fe to + 2 in FeCl2, and the oxidation state of hydrogen
changes from + 1 in HCl to 0 in H 2. Thus, iron is oxidized and hydrogen is reduced.
Solve

Fe1s2 ¡ Fe 2+ 1aq2 + 2 e -
The balanced chemical equations are as follows.

2 H +1aq2 + 2 e - ¡ H 21g2
Oxidation:

Fe1s2 + 2 H +1aq2 ¡ Fe 2+ 1aq2 + H 21g2

Reduction:
Overall:
Assess
This example illustrates that iron dissolves in acid solution. Iron is a major component of steel and the reaction
in this example contributes to the corrosion of steel that is exposed to air and moisture. For example, H + ions
from acid rain cause Fe atoms in steel to become oxidized to Fe 2+ ions. The oxidation of iron creates small pits
in the steel surface and leads to corrosion.
 5-4 Oxidation Reduction Reactions: Some General Principles 169

(a) (b) (c)

FIGURE 5-13
Displacement of H* (aq) by iron Example 5-5 illustrated
(a) An iron nail is wrapped in a piece of copper screen. (b) The nail and screen

reacts completely and produces Fe2+1aq2, but the copper does not react.
are placed in HCl(aq). Hydrogen gas is evolved as the nail reacts. (c) The nail

Represent the reaction of aluminum with hydrochloric acid to produce AlCl31aq2 and
H 21g2 by oxidation and reduction half-equations and an overall equation.
PRACTICE EXAMPLE A:

PRACTICE EXAMPLE B: Represent the reaction of chlorine gas with aqueous sodium bromide to produce liquid
bromine and aqueous sodium chloride by oxidation and reduction half-equations and an overall equation.

Even now, you can probably see that the answers to these questions lie in the
relative abilities of Fe and Cu atoms to give up electrons to become oxidized.
Fe gives up electrons more easily than does Cu; also, Fe is more readily oxi-
dized to Fe 2+ than it is to Fe 3+. We can give more complete answers after we
develop specific criteria describing electron loss and gain in Chapter 20. For

mon metals that react with acids to displace H 21g2 and a few that do not. As
now, the information in Table 5.4 should be helpful. The table lists some com-

will react with cold water to produce H 21g2 and a solution of the metal
noted in the table, most of the group 1 and 2 metals are so reactive that they

hydroxide.

TABLE 5.4 Behavior of Some Common Metals

with Nonoxidizing Acidsa

React to Produce H21g2 Do Not React

Alkali metals (group 1)b Cu, Ag, Au, Hg

Alkaline earth metals (group 2)b
Al, Zn, Fe, Sn, Pb
aA nonoxidizing acid (for example, HCl, HBr, HI) is one in which the only possi-
ble reduction half-reaction is the reduction of H + to H 2. Additional possibilities
for metal acid reactions are considered in Chapter 20.

with cold water to produce H 21g2; the metal hydroxide is the other product.
bWith the exception of Be and Mg, all group 1 and group 2 metals also react
170 Chapter 5 Introduction to Reactions in Aqueous Solutions

5-4 CONCEPT ASSESSMENT

Disregarding the fact that the equations below are not balanced, is it likely that

(a) MnO4 -1aq2 + Cr2O7 2-1aq2 + H+1aq2 ¡ MnO21s2 + Cr3+ 1aq2 + H2O1l2
either represents a reaction that could possibly occur? Explain.

(b) Cl21g2 + OH-1aq2 ¡ Cl-1aq2 + ClO3-1aq2 + H2O1l2

5-5 Balancing Oxidation Reduction

Equations
Half-reaction or half- In a chemical reaction, atoms are neither created nor lost; they are simply
*

equation, which is it? Reaction rearranged. We used this idea in Chapter 4 to balance chemical equations by
refers to the actual process. inspection. In a redox reaction, we have additional considerations. Electrons
An equation is a notation we are transferred from one substance to another and so we must keep track of
write out to indicate the electrons and the charge that these electrons carry. Therefore, in balancing the
formulas of the reactants chemical equation for a redox reaction, we focus equally on three factors:
and products, and their mole
(1) the number of atoms of each type, (2) the number of electrons transferred,
relationships. Many chemists
refer to what we balance here
and (3) the total charges on reactants and products. We should point out, how-
as half-reactions but ever, that if we balance the equation with respect to the number of atoms and
half-equation is more the number of electrons transferred, then the equation is automatically bal-
proper. anced with respect to the total charges.
Because it is very challenging to deal with all three of these factors simul-
taneously, only a small proportion of oxidation reduction equations can be
balanced by simple inspection. To make this point clear, consider the follow-
ing reactions, each of which appears to be balanced. The reactions are bal-
anced with respect to the number of atoms of each type and the total charges
on reactants and products, but not with respect to the number of electrons
transferred.
For brevity, the physical 2 MnO4 - + H2O2 + 6 H+ ¡ 2 Mn2+ + 3 O2 + 4 H2O (5.19)
*

forms of reactants and prod- - +

2 MnO4 + 3 H2O2 + 6 H ¡ 2 Mn 2+
+ 4 O2 + 6 H2O (5.20)
ucts are not included in these
equations. For all ions, as 2 MnO4 - + 5 H2O2 + 6 H+ ¡ 2 Mn2+ + 5 O2 + 8 H2O (5.21)
- + 2+
well as H2O2, the physical 2 MnO4 + 7 H2O2 + 6 H ¡ 2 Mn + 6 O2 + 10 H2O (5.22)
form is (aq). Of course, the
physical forms of oxygen and These are just a few of the balanced chemical equations we can write for the
water are O2(g) and H2O(l). reaction. However, only one, equation (5.21), is properly balanced because it is
the only one that is balanced with respect to the number of electrons transferred.
To balance the chemical equation for a redox reaction, we need to make use
of a systematic approach that considers each of the relevant factors in turn.
Although several methods are available, we emphasize one that focuses first
on balancing separate half-equations and then on combining the two half-
equations to obtain the overall chemical equation. The method is summarized
below. An alternative method is described in Exercise 98.

The Half-Equation Method

The basic steps in this method of balancing a redox equation are as follows:
Write and balance separate half-equations for oxidation and reduction.
Adjust coefficients in the two half-equations so that the same number of
electrons appear in each half-equation.
Add together the two half-equations (canceling out electrons) to obtain
the balanced overall equation.
 5-5 Balancing Oxidation Reduction Equations 171

TABLE 5.5 Balancing Equations for Redox Reactions in Acidic

Aqueous Solutions by the Half-Equation Method: A Summary
Write the equations for the oxidation and reduction half-reactions.
In each half-equation
(1) Balance atoms of all the elements except H and O
(2) Balance oxygen by using H2O
(3) Balance hydrogen by using H+
(4) Balance charge by using electrons
If necessary, equalize the number of electrons in the oxidation and reduction half-
equations by multiplying one or both half-equations by appropriate integers.
Add the half-equations, then cancel species common to both sides of the overall
equation.
Check that both numbers of atoms and charges balance.

This first step in this method actually involves several steps. A detailed
description of the method is given in Table 5.5. The method is appropriate for
reactions that occur in an acidic solution. Because an acidic solution contains
an excess of H + ions, the method uses H + ions in balancing the half-equations.

EXAMPLE 5-6 Balancing the Equation for a Redox Reaction in an Acidic Solution

The reaction described by expression (5.23) below is used to determine the sulfite ion concentration present in
wastewater from a papermaking plant. Use the half-equation method to obtain a balanced equation for this

SO3 2-1aq2 + MnO4 -1aq2 ¡ SO4 2-1aq2 + Mn2+1aq2

reaction in an acidic solution.
(5.23)
Analyze
The reaction occurs in acidic aqueous solution. We can use the method summarized in Table 5.5 to balance it.
Solve
The O.S. of sulfur increases from + 4 in SO3 2- to + 6 in SO4 2-. The O.S. of Mn decreases from + 7 in MnO4 - to
+ 2 in Mn2+. Thus, SO 3 2- is oxidized and MnO4 - is reduced.

SO3 2- 1aq2 ¡ SO4 2- 1aq2

Step 1. Write skeleton half-equations based on the species undergoing oxidation and reduction. The half-equations are

MnO4 -1aq2 ¡ Mn2+1aq2

Step 2. Balance each half-equation for numbers of atoms, in this order:
atoms other than H and O
O atoms, by adding H 2O with the appropriate coefficient
H atoms, by adding H + with the appropriate coefficient
The other atoms (S and Mn) are already balanced in the half-equations. To balance O atoms, we add

SO3 2-1aq2 + H 2O1l2 ¡ SO4 2-1aq2

one H 2O molecule to the left side of the first half-equation and four to the right side of the second.

MnO 4 -1aq2 ¡ Mn2+ 1aq2 + 4 H 2O1l2

To balance H atoms, we add two H + ions to the right side of the first half-equation and eight to the

SO3 2-1aq2 + H 2O1l2 ¡ SO4 2-1aq2 + 2 H +1aq2

left side of the second.

MnO 4 -1aq2 + 8 H +1aq2 ¡ Mn2+1aq2 + 4 H 2O1l2

(continued)
172 Chapter 5 Introduction to Reactions in Aqueous Solutions

Step 3. Balance each half-equation for electric charge. Add the number of electrons necessary to get the same elec-
tric charge on both sides of each half-equation. By doing this, you will see that the half-equation in
which electrons appear on the right side is the oxidation half-equation. The other half-equation, with

SO3 2-1aq2 + H 2O1l2 ¡ SO4 2-1aq2 + 2 H +1aq2 + 2 e -

electrons on the left side, is the reduction half-equation.

1net charge on each side, - 22

Oxidation:

MnO4 -1aq2 + 8 H +1aq2 + 5 e - ¡ Mn2+1aq2 + 4 H 2O1l2

1net charge on each side, + 22
Reduction:

Step 4. Obtain the overall redox equation by combining the half-equations. Multiply the oxidation half-equation by
5 and the reduction half-equation by 2. This results in 10 e - on each side of the overall equation. These
terms cancel out. Electrons must not appear in the final equation.

5 SO 3 2-(aq2 + 5 H 2O1l2 ¡ 5 SO4 2-1aq2 + 10 H +1aq2 + 10 e -

Overall:

2 MnO4 -1aq2 + 16 H +1aq2 + 10 e - ¡ 2 Mn2+ 1aq2 + 8 H 2O1l2

5 SO 3 2-1aq2 + 2 MnO4 -1aq2 + 5 H 2O1l2 + 16 H +1aq2 ¡
5 SO4 2-1aq2 + 2 Mn2+1aq2 + 8 H 2O1l2 + 10 H +1aq2
Step 5. Simplify. The overall equation should not contain the same species on both sides. Subtract 5 H 2O
from each side of the equation in step 4. This leaves 3 H 2O on the right. Also subtract 10 H + from each

5 SO 3 2-1aq2 + 2 MnO 4 -1aq2 + 6 H +1aq2 ¡ 5 SO4 2-1aq2 + 2 Mn2+1aq2 + 3 H 2O1l2

side, leaving 6 H + on the left.

Step 6. Verify. Check the overall equation to ensure that it is balanced both for numbers of atoms and electric

equation is - 6: 15 * 2 - 2 + 12 * 1 - 2 + 16 * 1 + 2 = 15 * 2 - 2 + 12 * 2 + 2 = - 6.
charge. For example, show that in the balanced equation from step 5, the net charge on each side of the

Assess
The final check completed in step 6 gives us confidence that our result is correct. This is an important step;
always take the time to complete it. It is also worth pointing out that, in this example, there was only one atom
per formula that was oxidized or reduced. (Refer to the skeleton half-equations given in step 1.) Many stu-
dents have difficulty balancing half-equations in which more than one atom per formula is oxidized or
reduced, as is the case when Cr2O7 2- is reduced to Cr 3+. Had we used Cr2O7 2- instead of MnO4 - in equation
(5.23), the balanced chemical equation for the reaction would have been 3 SO3 2- + Cr2O7 2- + 8 H + :
3 SO 4 2- + 2 Cr 3+ + 4 H 2O.

Fe 2+1aq2 + MnO4 -1aq2 ¡ Fe 3+ 1aq2 + Mn2+1aq2

PRACTICE EXAMPLE A: Balance the equation for this reaction in acidic solution.

UO 2+1aq2 + Cr2O7 2-1aq2 ¡ UO2 2+1aq2 + Cr 3+1aq2

PRACTICE EXAMPLE B: Balance the equation for this reaction in acidic solution.

Balancing Redox Equations in a Basic Solution

To balance equations for redox reactions in a basic solution, a step or two must be
added to the procedure used in Example 5-6. The problem is that in basic solu-
tion, OH -, not H +, must appear in the final balanced equation. (Recall that,
in basic solutions, OH - ions are present in excess.) Because both OH - and
H 2O contain H and O atoms, at times it is hard to decide on which side of the
half-equations to put each one. One simple approach is to treat the reaction as
though it were occurring in an acidic solution, and balance it as in Example 5-6.
Then, add to each side of the overall redox equation a number of OH - ions equal
to the number of H + ions. Where H + and OH - appear on the same side of the
equation, combine them to produce H 2O molecules. If H 2O now appears on
both sides of the equation, subtract the same number of H 2O molecules from
each side, leaving a remainder of H 2O on just one side. This method is illustrated
in Example 5-7. For ready reference, the procedure is summarized in Table 5.6.
 5-5 Balancing Oxidation Reduction Equations 173

EXAMPLE 5-7 Balancing the Equation for a Redox Reaction in Basic Solution

basic solution, and the permanganate is itself reduced to MnO21s2.

Balance the equation for the reaction in which cyanide ion is oxidized to cyanate ion by permanganate ion in a

MnO4 -1aq2 + CN -1aq2 ¡ MnO21s2 + OCN -1aq2 (5.24)

Analyze
The reaction occurs in basic solution. We can balance it by using the method described in Table 5.6 on the next
page. The half-reactions and the overall reaction are initially treated as though they were occurring in an acidic
solution and, finally, the overall equation is adjusted to a basic solution.
Solve

MnO4 -1aq2 ¡ MnO21s2

Step 1. Write half-equations for the oxidation and reduction half-reactions, and balance them for Mn, C, and N atoms.

CN -1aq2 ¡ OCN -1aq2

Step 2. Balance the half-equations for O and H atoms. Add H2O and/or H+ as required. In the MnO4 - half-equation,
there are four O s on the left and two on the right. Adding 2 H2O balances the O s on the right. Since
there are now four H s on the right, it is necessary to add 4 H+ on the left side to balance them. In the
CN- half-equation, there is one O on the right but none on the left, so H2O must be added to the left

MnO4 -1aq2 + 4 H +1aq2 ¡ MnO21s2 + 2 H 2O1l2

side and 2 H+ to the right.

CN -1aq2 + H 2O1l2 ¡ OCN -1aq2 + 2 H +1aq2

MnO 4 -1aq2 + 4 H +1aq2 + 3 e - ¡ MnO21s2 + 2 H 2O1l2

Step 3. Balance the half-equations for electric charge by adding the appropriate numbers of electrons.

CN -1aq2 + H 2O1l2 ¡ OCN -1aq2 + 2 H +1aq2 + 2 e -

Reduction:
Oxidation:
Step 4. Combine the half-equations to obtain an overall redox equation. Multiply the reduction half-equation by
two and the oxidation half-equation by three to obtain the common multiple 6 e- in each half-
equation. Make the appropriate cancellations of H+ and H2O.
2 MnO 4 -1aq2 + 8 H +1aq2 + 6 e - ¡ 2 MnO 21s2 + 4 H 2O1l2
3 CN -1aq2 + 3 H 2O1l2 ¡ 3 OCN -1aq2 + 6 H +1aq2 + 6 e -
Overall: 2 MnO 4 -1aq2 + 3 CN -1aq2 + 2 H +1aq2 ¡
2 MnO21s2 + 3 OCN -1aq2 + H 2O1l2
Step 5. Change from an acidic to a basic medium by adding 2 OH- to both sides of the overall equation; combine 2 H +

2 MnO 4 -1aq2 + 3 CN -1aq2 + 2 H +1aq2 + 2 OH -1aq2 ¡

and 2 OH - to form 2 H2O, and simplify.

2 MnO 21s2 + 3 OCN -1aq2 + H 2O1l2 + 2 OH -1aq2

2 MnO 4-1aq2 + 3 CN -1aq2 + 2 H 2O1l2 ¡ 2 MnO 21s2 + 3 OCN -1aq2 + H 2O1l2 + 2 OH -1aq2
Subtract one H2O molecule from each side to obtain the overall balanced redox equation for

2 MnO4 -1aq2 + 3 CN -1aq2 + H 2O1l2 ¡ 2 MnO21s2 + 3 OCN -1aq2 + 2 OH -1aq2

reaction (5.24).

Step 6. Verify. Check the final overall equation to ensure that it is balanced both for number of atoms and for
electric charge. For example, show that in the balanced equation from step 5, the net charge on each
side of the equation is - 5.
Assess
We can use the rules for assigning oxidation states (given in Table 3.2) to deduce that manganese is reduced
from + 7 in MnO4 - to + 4 in MnO2. We conclude that the other substance, CN -, is oxidized. (The rules do not
allow us to assign oxidation states to C and N in CN - or CNO -.) Even though we cannot identify the oxidation
states of C or N, we could still balance the equation for the reaction. That is one advantage of the methods we
presented in Tables 5-5 and 5-6. In Chapter 10, we will discuss another method for assigning oxidation states
and learn how to determine the oxidation states of C and N in such species as CN - or CNO -.
(continued)
174 Chapter 5 Introduction to Reactions in Aqueous Solutions

S1s2 + OCl-1aq2 ¡ SO3 2-1aq2 + Cl -1aq2

PRACTICE EXAMPLE A: Balance the equation for this reaction in basic solution.

MnO4 -1aq2 + SO3 2-1aq2 ¡ MnO21s2 + SO4 2- 1aq2

PRACTICE EXAMPLE B: Balance the equation for this reaction in basic solution.

As an alternative method TABLE 5.6 Balancing Equations for Redox Reactions in Basic
for half-equations in basic Aqueous Solutions by the Half-Equation Method: A Summary
solutions, add two OH - for
every O required to the Balance the equation as if the reaction were occurring in acidic medium by
O-deficient side, and add one using the method for acidic aqueous solutions summarized in Table 5-5.
H 2O to the other side (the net Add a number of OH - ions equal to the number of H + ions to both sides of the
effect is adding one O to the overall equation.
O-deficient side). Then add On the side of the overall equation containing both H + and OH - ions, combine
one H 2O for every H required them to form H 2O molecules. If H 2O molecules now appear on both sides
to the H-deficient side, and of the overall equation, cancel the same number from each side, leaving a
add one OH - to the other side remainder of H 2O on just one side.
(the net effect is adding one Check that both numbers of atoms and charges balance.
H to the H-deficient side).

Disproportionation Reactions
In some oxidation reduction reactions, called disproportionation reactions,
the same substance is both oxidized and reduced. An example is the decom-

2 H 2O21aq2 ¡ 2 H 2O1l2 + O 21g2

postion of hydrogen peroxide, H 2O2, into H 2O and O 2:
(5.25)

- 2 in H 2O (a reduction) and to 0 in O21g2 (an oxidation). H 2O2 is both oxi-

In reaction (5.25), the oxidation state of oxygen changes from - 1 in H 2O 2 to

dized and reduced. Reaction (5.25) produces O21g2, which bubbles out of the
solution. (See Figure 5-14.)
Another example is the disproportionation of S 2O 32- in acid solution:
S 2O 3 2-1aq2 + 2 H +1aq2 ¡ S1s2 + SO21g2 + H 2O1l2 (5.26)
The oxidation states of S are + 2 in S 2O 3 , 0 in S, and + 4 in SO2. Thus, S 2O 32-
2-

1Na 2S 2O32 are often used in the laboratory in redox reactions, and stock solu-
is simultaneously oxidized and reduced. Solutions of sodium thiosulfate

tions of Na 2S 2O3 sometimes develop small deposits of sulfur, a pale yellow

solid, over time.
The same substance appears on the left side in each half-equation for a dis-
proportionation reaction. The balanced half-equations and overall equation
FIGURE 5-14

S 2O3 2-1aq2 + H 2O1l2 ¡ 2 SO 21g2 + 2 H +1aq2 + 4 e -

for reaction (5.26) are given below.
Antiseptic action of

S 2O3 1aq2 + 6 H +1aq2 + 4 e - ¡ 2 S1s2 + 3 H 2O1l2

hydrogen peroxide Oxidation:

2 S 2O3 2-1aq2 + 4 H +1aq2 ¡ 2 S1s2 + 2 SO21g2 + 2 H 2O1l2

solution Reduction: 2-
Dilute aqueous solutions of

S 2O3 2- 1aq2 + 2 H +1aq2 ¡ S1s2 + SO21g2 + H 2O1l2

hydrogen peroxide (usually
3% hydrogen peroxide by Overall:
mass) were once commonly
used to clean minor cuts
and scrapes. A solution of
hydrogen peroxide bubbles
5-5 CONCEPT ASSESSMENT
when poured over a cut
because of the production Is it possible for two different reactants in a redox reaction to yield a single
of gaseous oxygen. product? Explain.
 5-6 Oxidizing and Reducing Agents 175

5-2 ARE YOU WONDERING...

How to balance the equation for a redox reaction that
occurs in a medium other than an aqueous solution?
An example of such a reaction is the oxidation of NH 31g2 to NO(g), the first step

NH 31g2 + O21g2 ¡ NO1g2 + H 2O1g2

in the commercial production of nitric acid.

Some people prefer a method called the oxidation-state change method (see below) for
reactions of this type, but the half-equation method works just as well. All that is
needed is to treat the reaction as if it were occurring in an aqueous acidic solution;
H + should appear as both a reactant and a product and cancel out in the overall

45NH 3 + H 2O ¡ NO + 5 H + + 5 e -6
equation, as seen below.
Oxidation:
Reduction: 55O2 + 4 H + + 4 e - ¡ 2 H 2O6
Overall: 4 NH 3 + 5 O2 ¡ 4 NO + 6 H 2O

Oxidation-state change method

In this method, changes in oxidation states are identified. That of nitrogen
increases from - 3 in NH 3 to + 2 in NO, corresponding to a loss of five electrons
per N atom. That of oxygen decreases from 0 in O2 to - 2 in NO and H 2O, corre-
sponding to a gain of two electrons per O atom. The proportion of N to O atoms
must be 2 N (loss of 10 e - ) to 5 O (gain of 10 e - ).
5
2 NH 3 + O2 ¡ 2 NO + 3 H 2O or 4 NH 3 + 5 O2 ¡ 4 NO + 6 H 2O
2

5-6 Oxidizing and Reducing Agents

Chemists frequently use the terms oxidizing agent and reducing agent to describe
certain of the reactants in redox reactions, as in statements like fluorine gas is
a powerful oxidizing agent, or calcium metal is a good reducing agent. Let
us briefly consider the meaning of these terms.
In a redox reaction, the substance that makes it possible for some other sub-
stance to be oxidized is called the oxidizing agent, or oxidant. In doing so, the
oxidizing agent is itself reduced. Similarly, the substance that causes some
other substance to be reduced is called the reducing agent, or reductant. In
the reaction, the reducing agent is itself oxidized. Or, stated in other ways,
An oxidizing agent (oxidant)
causes another substance to be oxidized
contains an element whose oxidation state decreases in a redox reaction
gains electrons (electrons are found on the left side of its half-equation)
is reduced
A reducing agent (reductant)
causes another substance to be reduced
contains an element whose oxidation state increases in a redox reaction
loses electrons (electrons are found on the right side of its half-equation)
is oxidized
In general, a substance with an element in one of its highest possible oxida-
tion states is an oxidizing agent. If the element is in one of its lowest possible
oxidation states, the substance is a reducing agent.
176 Chapter 5 Introduction to Reactions in Aqueous Solutions

Species O.S.

NO3+ *5
This species N2O4 *4
cannot be oxidized
further. NO2+ *3

NO *2
FIGURE 5-15 N2O *1
Oxidation states of nitrogen: Identifying oxidizing
and reducing agents N2 0
In NO3 - and N2O4, nitrogen is in one of its highest
possible oxidation states (O.S). These species are usually This species NH2OH +1
oxidizing agents in redox reactions. In N2H4 and NH3, cannot be reduced
further. N2H4 +2
nitrogen is in one of its lowest oxidation states. These
species are usually reducing agents. NH3 +3

Figure 5-15 shows the range of oxidation states of nitrogen and the species to

ide 1N2O42 is nearly the maximum value attainable, and hence N2O4 is gener-
which they correspond. The oxidation state of the nitrogen in dinitrogen tetrox-

ally an oxidizing agent. Conversely, the nitrogen atom in hydrazine 1N2H 42 is

in nearly the lowest oxidation state, and hence hydrazine is generally a reduc-
ing agent. When these two liquid compounds are mixed, a vigorous reaction

N2O41l2 + 2 N2H 41l2 ¡ 3 N21g2 + 4 H 2O1g2

takes place:

In this reaction, N2O4 is the oxidizing agent and N2H 4 is the reducing agent.
This reaction releases so much energy that it is used in some rocket propul-
sion systems.
Certain substances in which the oxidation state of an element is between its
highest and lowest possible values may act as oxidizing agents in some instances
and reducing agents in others. For example, in the reaction of hydrazine with

N2H 41l2 + H 21g2 ¡ 2 NH 31g2

hydrogen to produce ammonia, hydrazine acts as an oxidizing agent.

Permanganate ion, MnO4 -, is a versatile oxidizing agent that has many

uses in the chemical laboratory. In the next section, we describe its use in the

tive) amount of iron in an iron-containing material. Ozone, O 31g2, a triatomic

quantitative analysis of iron that is, the determination of the exact (quantita-

form of oxygen, is an oxidizing agent used in water purification, as in the oxi-

C6H 5OH1aq2 + 14 O31g2 ¡ 6 CO21g2 + 3 H 2O1l2 + 14 O21g2

dation of the organic compound phenol, C6H 5OH.
FIGURE 5-16
Bleaching action
of NaOCl(aq) Aqueous sodium hypochlorite, NaOCl(aq), is a powerful oxidizing agent. It
A red cloth becomes white is the active ingredient in many liquid chlorine bleaches. The bleaching action
when immersed in NaOCl(aq),
of NaOCl(aq) is associated with the reduction of the OCl - ion to Cl -; the elec-
which oxidizes the red
trons required for the reduction come from colored compounds in stains. The
pigment to colorless products.
bleaching action of NaOCl(aq) is demonstrated in Figure 5-16.
Thiosulfate ion, S 2O 3 2-, is an important reducing agent. One of its industrial

S 2O 3 2-1aq2 + 4 Cl21aq2 + 5 H 2O1l2 ¡ 2 HSO 4 - 1aq2 + 8 H +1aq2 + 8 Cl -1aq2

uses is as an antichlor to destroy residual chlorine from the bleaching of fibers.

Oxidizing and reducing agents also play important roles in biological

systems in photosynthesis (using solar energy to synthesize glucose),
metabolism (oxidizing glucose), and the transport of oxygen.
 5-7 Stoichiometry of Reactions in Aqueous Solutions: Titrations 177

EXAMPLE 5-8 Identifying Oxidizing and Reducing Agents

Hydrogen peroxide, H 2O2, is a versatile chemical. Its uses include bleaching wood pulp and fabrics
and substituting for chlorine in water purification. One reason for its versatility is that it can be either an
oxidizing or a reducing agent. For the following reactions, identify whether hydrogen peroxide is an oxidizing

(a) H 2O21aq2 + 2 Fe 2+1aq2 + 2 H +1aq2 ¡ 2 H 2O1l2 + 2 Fe 3+1aq2

or reducing agent.

(b) 5 H 2O21aq2 + 2 MnO4 -1aq2 + 6 H +1aq2 ¡ 8 H 2O1l2 + 2 Mn2+1aq2 + 5 O21g2

Analyze
Before we can identify the oxidizing and reducing agents, we must first assign oxidation states, and then iden-
tify which substance is being oxidized and which substance is being reduced. The oxidizing agent causes
another substance to be oxidized. The reducing agent causes another substance to be reduced.
Solve
(a) Fe 2+ is oxidized to Fe 3+ and because H 2O2 makes this possible, it is an oxidizing agent. Viewed another
way, we see that the oxidation state of oxygen in H 2O2 is - 1. In H 2O, it is - 2. Hydrogen peroxide is
reduced and thereby acts as an oxidizing agent.
(b) MnO 4- is reduced to Mn2+, and H 2O2 makes this possible. In this situation, hydrogen peroxide is a
reducing agent. Or, the oxidation state of oxygen increases from - 1 in H 2O2 to 0 in O2. Hydrogen
peroxide is oxidized and thereby acts as a reducing agent.
Assess
The versatility of H 2O2 lies in its ability to act as an oxidizing agent and a reducing agent. When H 2O2 acts as

solution. When it acts as a reducing agent, it is oxidized to O21g2, as was the case in part (b).
an oxidizing agent, it is reduced to H 2O, in an acidic solution, as was the case in part (a), or to OH - in basic

Is H 21g2 an oxidizing or reducing agent in this reaction? Explain.

2 NO21g2 + 7 H 21g2 ¡ 2 NH 31g2 + 4 H 2O1g2

PRACTICE EXAMPLE A:

4 Au1s2 + 8 CN -1aq2 + O21g2 + 2 H 2O1l2 ¡ 4[Au1CN22]-1aq2 + 4 OH -1aq2

PRACTICE EXAMPLE B: Identify the oxidizing agent and the reducing agent in the reaction.

5-6 CONCEPT ASSESSMENT

A newspaper account of an accidental spill of hydrochloric acid in an area where

sodium hydroxide solution was also stored spoke of the potential hazardous
release of chlorine gas if the two solutions should come into contact. Was this
an accurate accounting of the hazard involved? Explain.

5-7 Stoichiometry of Reactions in Aqueous

Solutions: Titrations
If our objective is to obtain the maximum yield of a product at the lowest cost,
we would generally choose the most expensive reactant as the limiting reac-
tant and use excess amounts of the other reactants. This is the case in most
precipitation reactions. In some instances, as in determining the concentra-
tion of a solution, we may not be interested in the products of a reaction but
only in the relationship between two reactants. Then we have to carry out the
reaction in such a way that neither reactant is in excess. A method that has
long been used for doing this is known as titration. The glassware typically
used in a titration is shown in Figure 5-17.
A solution of one reactant is placed in a small beaker or flask. Another reac-
tant, also in solution and commonly referred to as titrant, is in a buret, a long,
178 Chapter 5 Introduction to Reactions in Aqueous Solutions

(a) (b) (c)

FIGURE 5-17
An acid base titration Example 5-9 illustrated
(a) A 5.00 mL sample of vinegar, a small quantity of water, and a few drops of
phenolphthalein indicator are added to a flask. (b) 0.1000 M NaOH from a previously
filled buret is slowly added. (c) As long as the acid is in excess, the solution in the flask
remains colorless. When the acid has been neutralized, an additional drop of NaOH(aq)
causes the solution to become slightly basic. The phenolphthalein indicator turns a
light pink. The first lasting appearance of the pink color is taken to be the equivalence
point of the titration.

The key to a successful graduated tube equipped with a stopcock valve. The second solution is slowly
acid base titration is in select- added to the first by manipulating the stopcock. Titration is a reaction carried
ing the right indicator. We out by the carefully controlled addition of one solution to another. The trick is
learn how to do this when we to stop the titration at the point where both reactants have reacted completely,
consider theoretical aspects of a condition called the equivalence point of the titration. Key to every titration
titration in Chapter 17. is that at the equivalence point, the two reactants have combined in stoichio-
metric proportions; both have been consumed, and neither remains in excess.
In modern chemical laboratories, appropriate measuring instruments are used
to signal when the equivalence point is reached. Still widely used, though, is a
technique in which a very small quantity of a substance added to the reaction
mixture changes color at or very near the equivalence point. Such substances are
called indicators. Figure 5-17 illustrates the neutralization of an acid by a base by
the titration technique. Calculations that use titration data are much the same as

Suppose we need a KMnO 41aq2 solution of exactly known molarity, close

those introduced in Section 4-3, and they are also illustrated in Example 5-9.

amount of KMnO41s2 and dissolving it in water. The solid is not pure, and its
to 0.020 M. We cannot prepare this solution by weighing out the required
Standardize means
determine the concentration actual purity (that is, the mass percent KMnO4) is not known. Conversely, we

an acid to yield Fe 2+1aq2. Fe 2+1aq2 is oxidized to Fe 3+1aq2 by KMnO 41aq2 in

of a solution, usually to
can obtain iron wire in essentially pure form and allow the wire to react with

an acidic solution. By determining the volume of KMnO41aq2 required to oxi-

three or four significant

dize a known quantity of Fe 2+1aq2, we can calculate the exact molarity of the
figures. It is not so important

KMnO41aq2. This procedure, which determines the exact molarity of a solu-

that the concentration be a
round number (as 0.1000 vs.
0.1035 M), but rather that the
concentration be accurately tion, is called standardization of a solution. It is illustrated in Example 5-10
known. and Figure 5-18.
 5-7 Stoichiometry of Reactions in Aqueous Solutions: Titrations 179

EXAMPLE 5-9 Using Titration Data to Establish the Concentrations of Acids and Bases

Vinegar is a dilute aqueous solution of acetic acid produced by the bacterial fermentation of apple cider, wine,
or other carbohydrate material. The legal minimum acetic acid content of vinegar is 4% by mass. A 5.00 mL
sample of a particular vinegar is titrated with 38.08 mL of 0.1000 M NaOH. Does this sample exceed the mini-
mum limit? (Vinegar has a density of about 1.01 g>mL.)
Analyze
Acetic acid, CH3COOH, is a weak acid and NaOH is a strong base. The reaction between CH3COOH and
NaOH is an acid base neutralization reaction. We start by writing a balanced chemical equation for the reac-
tion. We must convert mL NaOH to CH3COOH. The necessary conversions are as follows:
mL NaOH ¡ L NaOH ¡ mol NaOH ¡ mol CH3COOH ¡ g CH3COOH
Solve
The balanced chemical equation for the reaction is given below.
CH3COOH1aq2 + NaOH1aq2 ¡ NaCH3COO1aq2 + H2O1l2
1L 0.1000 mol NaOH
? g HC2H 3O2 = 38.08 mL * *
1000 mL 1L
1 mol CH3COOH 60.05 g CH 3COOH
* *
1 mol NaOH 1 mol CH3COOH
= 0.2287 g CH3COOH
This mass of CH 3COOH is found in 5.00 mL of vinegar of density 1.01 g>mL. The percent mass of CH3COOH is
0.2287 g CH3COOH 1 mL vinegar
% CH3COOH = * * 100%
5.00 mL vinegar 1.01 g vinegar
= 4.53% CH3COOH
The vinegar sample exceeds the legal minimum limit but only slightly. There is also a standard for the
maximum amount of acetic acid allowed in vinegar. A vinegar producer might use this titration technique to
ensure that the vinegar stays between these limits.
Assess
Such problems as this one involve many steps or conversions. Try to break the problem into simpler ones
involving fewer steps or conversions. It may also help to remember that solving a stoichiometry problem
involves three steps: (1) converting to moles, (2) converting between moles, and (3) converting from moles. Use
molarities and molar masses to carry out volume mole conversions and gram mole conversions, respectively,
and stoichiometric factors to carry out mole mole conversions. The stoichiometric factors are constructed from
a balanced chemical equation.

PRACTICE EXAMPLE A: A particular solution of NaOH is supposed to be approximately 0.100 M. To determine

the exact molarity of the NaOH(aq), a 0.5000 g sample of KHC8H 4O4 is dissolved in water and titrated with

HC8H 4O4 -1aq2 + OH -1aq2 ¡ C8H 4O4 2- 1aq2 + H 2O1l2

24.03 mL of the NaOH(aq). What is the actual molarity of the NaOH(aq)?

PRACTICE EXAMPLE B: A 0.235 g sample of a solid that is 92.5% NaOH and 7.5% Ca1OH22, by mass, requires
45.6 mL of a HCl(aq) solution for its titration. What is the molarity of the HCl(aq)?

5-7 CONCEPT ASSESSMENT

A 10.00 mL sample of 0.311 M KOH is added to 31.10 mL of 0.100 M HCl.

Is the resulting mixture acidic, basic, or exactly neutral? Explain.
180 Chapter 5 Introduction to Reactions in Aqueous Solutions

(a) (b) (c)

FIGURE 5-18
Standardizing a solution of an oxidizing agent through a redox
titration Example 5-10 illustrated

intensely colored KMnO41aq2 to be standardized. (b) As it is added to the strongly

(a) The solution contains a known amount of Fe2+, and the buret is filled with the

acidic solution of Fe2+1aq2, the KMnO41aq2 is immediately decolorized as a result of

reaction (5.27). (c) When all the Fe2+ has been oxidized to Fe3+, additional KMnO41aq2

of a drop of the KMnO41aq2 beyond the equivalence point is sufficient to cause this
has nothing left to oxidize and the solution turns a distinctive pink. Even a fraction

pink coloration.

EXAMPLE 5-10 Standardizing a Solution for Use in Redox Titrations

A piece of iron wire weighing 0.1568 g is converted to Fe2+1aq2 and requires 26.24 mL of a KMnO41aq2 solution
for its titration. What is the molarity of the KMnO41aq2?
5 Fe 2+1aq2 + MnO4 -1aq2 + 8 H +1aq2 ¡ 5 Fe 3+ 1aq2 + Mn2+1aq2 + 4 H 2O1l2 (5.27)
Analyze
The key to a titration calculation is that the amounts of two reactants consumed in the titration are stoichiomet-
rically equivalent neither reactant is in excess. We are given an amount of Fe (0.156 g) and must determine the
number of moles of KMnO4 in the 26.24 mL sample. The following conversions are required:
g Fe ¡ mol Fe ¡ mol Fe 2+ ¡ mol MnO 4 - ¡ mol KMnO4
The third conversion, from mol Fe2+ to mol MnO 4 - , requires a stoichiometric factor constructed from the coef-
ficients in equation (5.27).
Solve
First, determine the amount (in moles) of KMnO4 consumed in the titration.
1 mol Fe 1 mol Fe2+
? mol KMnO4 = 0.1568 g Fe * *
55.847 g Fe 1 mol Fe
1 mol MnO4 - 1 mol KMnO4
* *
5 mol Fe 2+ 1 mol MnO4 -
= 5.615 * 10-4 mol KMnO4
 Summary 181

The volume of solution containing the 5.615 * 10-4 mol KMnO4 is 26.24 mL = 0.02624 L, which means that
5.615 * 10-4 mol KMnO4
concn KMnO4 = = 0.02140 M KMnO4
0.02624 L
Assess
For practical applications, such as for titrations, we use solutions with molarities that are neither very large nor
very small. Typically, the molarities lie in the range 0.001 M to 0.1 M. If you calculate a molarity that is signifi-
cantly larger than 0.1 M, or significantly smaller than 0.001 M, then you must carefully check your calculation
for possible errors.

PRACTICE EXAMPLE A: A 0.376 g sample of an iron ore is dissolved in acid, and the iron reduced to Fe2+1aq2
and then titrated with 41.25 mL of 0.02140 M KMnO4. Determine the mass percent Fe in the iron ore.
[Hint: Use equation (5.27).]

Another substance that may be used to standardize KMnO41aq2 is sodium oxalate. If

0.2482 g Na2C2O4 is dissolved in water and titrated with 23.68 mL KMnO4, what is the molarity of the KMnO41aq2?
PRACTICE EXAMPLE B:

MnO4 -1aq2 + C2O4 2-1aq2 + H +1aq2 ¡ Mn2+1aq2 + H2O1l2 + CO21g2 1not balanced2

www.masteringchemistry.com

Access to a plentiful supply of pure water is something most of us take for granted. Still,
most of us would agree that purification of water is an important concern. The way in which
water is purified depends on how it is to be used or on how it has been used. For a discussion
of the removal or destruction of undesirable chemical substances from water, go to the Focus
On feature for Chapter 5, entitled Water Treatment, on the MasteringChemistry site.

Summary
5-1 The Nature of Aqueous Solutions Solutes in theory, in an acid base reaction, protons are transferred
aqueous solution are characterized as nonelectrolytes, from the acid (the proton donor) to the base (the proton
which do not produce ions, or electrolytes, which pro- acceptor). In a typical acid base, or neutralization,
duce ions. Weak electrolytes dissociate to a limited extent, reaction, H + ions from the acid and OH - ions from the
and strong electrolytes dissociate almost completely into base combine to form HOH (water). The other product of
ions. In addition to the molarity based on the solute as a the reaction is an ionic compound, a salt. Some reactions
whole, a solution s concentration can be stated in terms of in which gases are evolved can also be treated as
the molarities of the individual solute species present acid base reactions (Table 5.3).
molecules and ions. Calculating ion concentrations in a
strong electrolyte solution is easily done. 5-4 Oxidation Reduction Reactions: Some
General Principles In an oxidation reduction (redox)
5-2 Precipitation Reactions Some reactions in reaction certain atoms undergo an increase in oxidation
aqueous solution involve the combination of ions to yield state, a process called oxidation. Other atoms undergo a
a water-insoluble solid a precipitate. Precipitation reac- decrease in oxidation state, or reduction. Another useful
tions are generally represented by net ionic equations, a view of redox reactions is as the combination of separate
form in which only the reacting ions and solid precipitates half-reactions for the oxidation and the reduction.
are shown, and spectator ions are deleted. Precipitation
reactions usually can be predicted by using a few simple 5-5 Balancing Oxidation Reduction Equations
solubility guidelines (Table 5.1). An effective way to balance a redox equation is to break
5-3 Acid Base Reactions According to the Arrhenius down the reaction into separate half-reactions, write and
theory, a substance that ionizes to produce H + ions in balance half-equations for these half-reactions, and recom-
aqueous solution is an acid. It is a strong acid (Table 5.2) bine the balanced half-equations into an overall balanced
if the ionization goes essentially to completion and a equation (Table 5.5). A slight variation of this method is
weak acid if the ionization is limited. Similarly, a base used for a reaction that occurs in a basic aqueous solution
produces OH - ions in aqueous solution and is either a (Table 5.6). A redox reaction in which the same substance is
strong base (Table 5.2) or a weak base, depending on the both oxidized and reduced is called a disproportionation
extent of the ionization. According to the Brønsted-Lowry reaction.
182 Chapter 5 Introduction to Reactions in Aqueous Solutions

5-6 Oxidizing and Reducing Agents The 5-7 Stoichiometry of Reactions in Aqueous
oxidizing agent (oxidant) is the key reactant in an oxida- Solutions: Titrations A common laboratory tech-
tion half-reaction and is reduced in the redox reaction. The nique applicable to precipitation, acid base, and redox
reducing agent (reductant) is the key reactant in a reduc- reactions is titration. The key point in a titration is the
tion half-reaction and is oxidized in the redox reaction. equivalence point, which is assessed with the aid of an
Some substances act only as oxidizing agents; others, only indicator. Titration data can be used to establish a solu-
as reducing agents. Many can act as either, depending on tion s molarity, called standardization of a solution, or to
the reaction (Fig. 5-15). provide other information about the compositions of sam-
ples being analyzed.

Integrative Example
Sodium dithionite, Na 2S 2O4, is an important reducing agent. One interesting use is the reduction of chromate ion to
insoluble chromium(III) hydroxide by dithionite ion, S 2O 4 2-, in basic solution. Sulfite ion is another product. The chro-

in a reaction with 100.0 L of wastewater having 3CrO 4 2-4 = 0.0148 M?

mate ion may be present in wastewater from a chromium-plating plant, for example. What mass of Na 2S 2O4 is consumed

a yellow solution of potassium chromate, K2CrO41aq2

White solid sodium dithionite, Na2S2O4, is added to
*

chromium(III) hydroxide, Cr1OH231s2 (right).

(left). A product of the reaction is gray-green

Analyze
The phrase reduction of chromate tells us that the reaction between CrO4 2- and S 2O4 2- is a redox reaction. We must
obtain a balanced chemical equation for the reaction by using the method summarized in Table 5.6, and then convert
100.0 L of wastewater into grams of Na 2S 2O4. The necessary conversions are as follows:
100.0 L wastewater ¡ mol CrO4 2- ¡ mol S 2O4 2- ¡ mol Na 2S 2O4 ¡ g Na 2S 2O4

CrO4 2-1aq2 + S 2O4 2- 1aq2 + OH -1aq2 ¡

Solve

Cr1OH231s2 + SO3 2-1aq2

1. Write an ionic expression representing the reaction.

2. Balance the redox equation. Begin by writing skele- CrO4 2- ¡ Cr1OH23

ton half-equations. S 2O4 2- ¡ SO3 2-

Balance the half-equations for Cr, S, O, and H atoms CrO4 2- + 5 H + ¡ Cr1OH23 + H 2O

as if the half-reactions occur in acidic solution. S 2O4 2- + 2 H 2O ¡ 2 SO3 2- + 4 H +

Balance the half-equations for charge, and label Oxidation: S 2O4 2- + 2 H 2O ¡ 2 SO 3 2- + 4 H + + 2 e -

them as oxidation and reduction. Reduction: CrO4 2- + 5 H + + 3 e - ¡ Cr1OH23 + H 2O

3 * 3S 2O4 2- + 2 H 2O ¡ 2 SO3 2- + 4 H + + 2 e -4
2 * 3CrO4 2- + 5 H + + 3 e - ¡ Cr1OH23 + H 2O4
Combine the half-equations into an overall
equation.
3 S 2O4 2- + 2 CrO4 2- + 4 H 2O ¡
6 SO 3 2- + 2 Cr1OH23 + 2 H +

3. Change the conditions to basic solution. Add 2 OH - 3 S 2O4 2- + 2 CrO4 2- + 4 H 2O + 2 OH - ¡

to each side of the equation for acidic solution, 6 SO3 2- + 2 Cr1OH23 + 2 H 2O
and combine 2 H + and 2 OH - to form 2 H 2O on
the right.

3 S 2O4 2-1aq2 + 2 CrO4 2- 1aq2 + 2 H 2O1l2 + 2 OH -1aq2 ¡

6 SO 3 2- 1aq2 + 2 Cr1OH231s2
Subtract 2 H 2O from each side of the equation to
obtain the final balanced equation.
 Exercises 183

4. Complete the stoichiometric calculation. The 0.0148 mol CrO4 2-

conversion pathway is ? g Na 2S 2O4 = 100.0 L *
1L
100.0 L waste water ¡ mol CrO4 2- ¡
3 mol S 2O4 2- 1 mol Na 2S 2O4
mol S 2O4 2- ¡ mol Na 2S 2O4 ¡ g Na 2S 2O4. * *
2 mol CrO4 2- 1 mol S 2O4 2-
174.1 g Na 2S 2O4
* = 387 g Na 2S 2O4
1 mol Na 2S 2O4
Assess
In solving this problem the major effort was to balance a redox equation for a reaction under basic conditions. This
allowed us to find the molar relationship between dithionite and chromate ions. The remainder of the problem was a
stoichiometry calculation for a reaction in solution, much like Example 4-11 (page 128). A quick check of the final result

1.5 1i.e., 100 * 0.01482, that the number of moles of S 2O4 2- is about 2.25 1i.e., 1.5 * 3>22, and that the mass of Na 2S 2O4 is
involves (1) ensuring that the redox equation is balanced, and (2) noting that the number of moles of CrO 4 2- is about

somewhat more than 350 1i.e., 2.25 * 1752.

The sample was dissolved in 50.00 mL of 0.09101 M Fe1NO 322 and the solution was acidified. The excess Fe 2+ was
PRACTICE EXAMPLE A: The amount of potassium chlorate, KClO 3, in a 0.1432 g sample was determined as follows.

back-titrated with 12.59 mL of 0.08362 M Ce1NO324 solution. What is the percentage by mass of KClO3 in the sample?

ClO3 -1aq2 + Fe 2+1aq2 : Cl -1aq2 + Fe 3+1aq2 (not balanced) and Fe 2+1aq2 + Ce 4+ 1aq2 : Fe3+1aq2 + Ce3+1aq2.
Chemical equations for the reactions involved are as follows:

in the sample to arsenous acid 1H 3AsO32, and then titrating H 3AsO3 with 23.77 mL of 0.02144 M KMnO4. What is the
PRACTICE EXAMPLE B: The amount of arsenic, As, in a 7.25 g sample was determined by converting all the arsenic

H 3AsO31aq2 + MnO4 -1aq2 : H 3AsO41aq2 + Mn2+1aq2.

percentage by mass of As in the sample? The unbalanced chemical equation for the titration reaction is

You ll find a link to additional self study questions in the study area on
www.masteringchemistry.com

Exercises
Strong Electrolytes, Weak Electrolytes, and Nonelectrolytes
1. Using information from this chapter, indicate whether whether the solute is a strong, weak, or nonelec-
each of the following substances in aqueous solution is trolyte; and which of these substances it is: sodium

(a) HC6H 5O; (b) Li 2SO 4; (c) MgI 2; (d) 1CH 3CH 222O;
a nonelectrolyte, weak electrolyte, or strong electrolyte. chloride, propionic acid, hypochlorous acid, ammo-
nia, barium bromide, ammonium chloride, methanol.
(e) Sr1OH22.
2. Select the (a) best and (b) poorest electrical conductors
from the following solutions, and explain the reason
for your choices: 0.10 M NH 3; 0.10 M NaCl; 0.10 M
CH3COOH (acetic acid); 0.10 M CH3CH2OH (ethanol).
3. What response would you expect in the apparatus of
Figure 5-4 if the solution tested were 1.0 M HCl? What
response would you expect if the solution were both

4. NH 31aq2 conducts electric current only weakly. The

1.0 M HCl and 1.0 M CH3COOH?
(a) (b) (c)
same is true for CH3COOH1aq2. When these solu-
tions are mixed, however, the resulting solution is a 6. After identifying the three substances represented by
good conductor. How do you explain this? the sketches in Exercise 5, sketch molecular views of
5. Sketches (a c) are molecular views of the solute in an aqueous solutions of the remaining four substances
aqueous solution. For each of the sketches, indicate listed.
184 Chapter 5 Introduction to Reactions in Aqueous Solutions

Ion Concentrations

each solution. (a) 3K +4 in 0.238 M KNO3; (b) 3NO3 - 4

7. Determine the concentration of the ion indicated in 13. Which of the following aqueous solutions has the

in 0.167 M Ca1NO322; (c) 3Al3+4 in 0.083 M Al21SO423;

highest concentration of K +? (a) 0.0850 M K 2SO4;

(d) 3Na+4 in 0.209 M Na 3PO4. tion having 8.1 mg K +>mL.

(b) a solution containing 1.25 g KBr>100 mL; (c) a solu-

8. Which solution has the greatest 3SO4 2-4: (a) 0.075 M 14. Which aqueous solution has the greatest 3H +4:

(d) 0.080 M Al21SO423; (e) 0.20 M CuSO4?

H 2SO 4; (b) 0.22 M MgSO 4; (c) 0.15 M Na 2SO4; (a) 0.011 M CH3COOH; (b) 0.010 M HCl; (c) 0.010 M
H 2SO4; (d) 1.00 M NH 3? Explain your choice.
9. A solution is prepared by dissolving 0.132 g 15. How many milligrams of MgI 2 must be added to

3OH -4 in this solution? 3I -4 = 0.1000 M?

Ba1OH22 # 8 H 2O in 275 mL of water solution. What is 250.0 mL of 0.0876 M KI to produce a solution with

are 3K +], [Mg 2+4, and 3Cl-4 in this solution? containing 12.0 mg K 2SO4>mL, what is 3K +4 in the
10. A solution is 0.126 M KCl and 0.148 M MgCl2. What 16. If 25.0 mL H 2O evaporates from 1.00 L of a solution

molarities. (a) 14.2 mg Ca2+>L; (b) 32.8 mg K +>100 mL; 17. Assuming the volumes are additive, what is the 3Cl -4
11. Express the following data for cations in solution as solution that remains?

(c) 225mg Zn2+>mL. in a solution obtained by mixing 225 mL of 0.625 M

ion content of 0.9 mg F ->L, the federal government s

12. What molarity of NaF(aq) corresponds to a fluoride KCl and 615 mL of 0.385 M MgCl2 ?

3NO 3 - 4 in a solution obtained by mixing 275 mL

18. Assuming the volumes are additive, what is the

of 0.283 M KNO3, 328 mL of 0.421 M Mg1NO322, and

recommended limit for fluoride ion in drinking
water?
784 mL of H 2O?

Predicting Precipitation Reactions

19. Complete each of the following as a net ionic equa- 23. What reagent solution might you use to separate the
tion, indicating whether a precipitate forms. If no cations in the following mixtures, that is, with one ion
reaction occurs, so state. appearing in solution and the other in a precipitate?
(a) Na+ + Br - + Pb 2+ + 2 NO 3 - ¡ [Hint: Refer to Table 5.1, and consider water also to be

(a) BaCl21s2 and MgCl21s2

(b) Mg 2+ + 2 Cl - + Cu2+ + SO 4 2- ¡ a reagent.]

(b) MgCO31s2 and Na 2CO31s2

(c) Fe 3+ + 3 NO 3 - + Na + + OH - ¡

(c) AgNO31s2 and Cu1NO3221s2

20. Complete each of the following as a net ionic equa-
tion. If no reaction occurs, so state.
(a) Ca2+ + 2 I - + 2 Na + + CO 3 2- ¡ 24. What reagent solution might you use to separate the
(b) Ba2+ + S 2- + 2 Na + + SO 4 2- ¡ cations in each of the following mixtures?

(a) PbSO41s2 and Cu1NO3221s2

(c) 2 K + + S 2- + Ca2+ + 2 Cl - ¡ [Hint: Refer to Exercise 23.]

(b) Mg1OH221s2 and BaSO41s2

21. Predict in each case whether a reaction is likely to

(a) HI1aq2 + Zn1NO3221aq2 ¡ (c) PbCO31s2 and CaCO31s2

occur. If so, write a net ionic equation.

(b) CuSO41aq2 + Na 2CO 31aq2 ¡ 25. You are provided with NaOH1aq2, K 2SO41aq2,
(c) Cu1NO3221aq2 + Na 3PO41aq2 ¡ Mg1NO3221aq2, BaCl21aq2, NaCl1aq2, Sr1NO3221aq2,
22. Predict in each case whether a reaction is likely to AgNO31aq2, and BaSO41s2. Write net ionic equations

(a) AgNO31aq2 + CuCl21aq2 ¡ reagents to obtain (a) SrSO41s2; (b) Mg1OH221s2;

occur. If so, write a net ionic equation. to show how you would use one or more of those

(b) Na 2S1aq2 + FeCl21aq2 ¡

(c) Na 2CO31aq2 + AgNO31aq2 ¡
(c) KCl(aq).
26. Write net ionic equations to show how you would use

(a) BaSO41s2; (b) AgCl(s); (c) KNO 31aq2.

one or more of the reagents in Exercise 25 to obtain

Acid Base Reactions

27. Complete each of the following as a net ionic equation. The essential neutralization products are CO2 and/or
If no reaction occurs, so state. H 2O. Write net ionic equations to represent the neu-
(a) Ba2+ + 2 OH- + CH3COOH ¡ tralizing action of the following popular antacids.
(b) H+ + Cl- + CH3CH2COOH ¡ (a) Alka-Seltzer (sodium bicarbonate)
(c) FeS1s2 + H + + I - ¡ (b) Tums (calcium carbonate)
(d) K + + HCO3 - + H + + NO3 - ¡ (c) milk of magnesia (magnesium hydroxide)
(e) Mg1s2 + H + ¡ (d) Maalox (magnesium hydroxide, aluminum

(e) Rolaids 3NaAl1OH22CO34

28. Every antacid contains one or more ingredients hydroxide)
capable of reacting with excess stomach acid (HCl).
 Exercises 185

29. In this chapter, we described an acid as a substance 31. Which solutions would you use to precipitate Mg 2+

choice. (a) KNO31aq2; (b) NH 31aq2; (c) H 2SO41aq2;

capable of producing H + and a salt as the ionic com- from an aqueous solution of MgCl2? Explain your

(d) HC2H 3O21aq2.

pound formed by the neutralization of an acid by a
base. Write ionic equations to show that sodium
hydrogen sulfate has the characteristics of both a salt 32. Determine which of the following react(s) with HCl(aq)
and an acid (sometimes called an acid salt). to produce a gas, and write a net ionic equation(s) for
30. A neutralization reaction between an acid and a base the reaction(s). (a) Na 2SO4; (b) KHSO3; (c) Zn1OH22;
is a common method of preparing useful salts. Give

could be prepared in this way: (a) 1NH 422HPO 4;

(d) CaCl2.
net ionic equations showing how the following salts

(b) NH 4NO 3; and (c) 1NH 422SO4.

Oxidation Reduction (Redox) Equations

33. Assign oxidation states to the elements involved in (c) Fe1OH221s2 + O21g2 ¡ Fe1OH231s2

CH3COO - + MnO21s2
the following reactions. Indicate which are redox reac- (d) CH 3CH 2OH + MnO 4 - ¡

(a) MgCO31s2 + 2 H +1aq2 ¡

tions and which are not.

Mg 2+1aq2 + H 2O1l2 + CO21g2

41. Balance these equations for disproportionation

(b) Cl21aq2 + 2 Br 1aq2 ¡ 2 Cl -1aq2 + Br21aq2 (a) Cl21g2 ¡ Cl - + ClO 3 - (basic solution)
reactions.

(c) Ag1s2 + 2 H +1aq2 + NO3 -1aq2 ¡

-

Ag +1aq2 + H 2O1l2 + NO21g2

(b) S 2O4 2- ¡ S 2O3 2- + HSO 3 - (acidic solution)

(d) 2 Ag 1aq2 + CrO 4 1aq2 ¡ Ag 2CrO41s2

42. Balance these equations for disproportionation

(a) MnO 4 2- ¡ MnO21s2 + MnO 4 - (basic solution)

+ 2-
reactions.

(a) Fe 3+1aq2 + MnO4 -1aq2 + H +1aq2 ¡ (b) P41s2 ¡ H 2PO 2 - + PH 31g2 (basic solution)
34. Explain why these reactions cannot occur as written.

Mn2+1aq2 + Fe 2+1aq2 + H 2O1l2 (c) S 81s2 ¡ S 2- + S 2O 3 2- (basic solution)

(b) H 2O21aq2 + Cl21aq2 ¡
ClO -1aq2 + O21g2 + H +1aq2
(d) As2S 3 + H 2O2 ¡ AsO 4 3- + SO 4 2-
43. Write a balanced equation for these redox reactions.
35. Complete and balance these half-equations. (a) The oxidation of nitrite ion to nitrate ion by per-
(a) SO 3 2- ¡ S 2O 3 2- (acidic solution) -
manganate ion, MnO 4 , in acidic solution ( MnO 4 -
(b) HNO3 ¡ N2O1g2 (acidic solution) 2+
ion is reduced to Mn ).
(c) Al1s2 ¡ Al1OH24 - (basic solution) (b) The reaction of manganese(II) ion and perman-
Indicate whether oxidation or reduction is involved. ganate ion in basic solution to form solid manganese
36. Complete and balance these half-equations. dioxide.
(a) C2O 4 2- ¡ CO2 (acidic solution) (c) The oxidation of ethanol by dichromate ion in

hyde 1CH 3CHO2, and water as products.

(b) Cr2O7 2- ¡ Cr 3+ (acidic solution) acidic solution, producing chromium(III) ion, acetalde-
(c) MnO4 - ¡ MnO2 (basic solution)
Indicate whether oxidation or reduction is involved. 44. Write a balanced equation for the redox reactions.
37. Balance these equations for redox reactions occurring (a) The reaction of aluminum metal with hydroiodic

(a) MnO 4 - + I - ¡ Mn2+ + I 21s2 (b) The reduction of vanadyl ion 1VO 2+2 to vanadic
in acidic solution. acid.

(b) BrO 3 - + N2H 4 ¡ Br - + N2 ion 1V 3+2 in acidic solution with zinc metal as the
(c) VO 4 3- + Fe 2+ ¡ VO 2+ + Fe 3+ reducing agent.
(d) UO 2+ + NO3 - ¡ UO 2 2+ + NO1g2 (c) The oxidation of methanol by chlorate ion in
38. Balance these equations for redox reactions occurring acidic solution, producing carbon dioxide gas, water,

(a) P41s2 + NO 3 - ¡ H 2PO 4 - + NO1g2

in acidic solution. and chlorine dioxide gas as products.
45. The following reactions do not occur in aqueous solu-
(b) S 2O 3 2- + MnO 4 - ¡ SO 4 2- + Mn2+ tions. Balance their equations by the half-equation

(a) CH 41g2 + NO1g2 ¡

(c) HS - + HSO 3 - ¡ S 2O 3 2- method, as suggested in Are You Wondering 5-2.

CO21g2 + N21g2 + H 2O1g2

(d) Fe 3+ + NH 3OH + ¡ Fe 2+ + N2O1g2

(b) H 2S1g2 + SO21g2 ¡ S 81s2 + H 2O1g2

39. Balance these equations for redox reactions in basic

(a) MnO 21s2 + ClO 3 - ¡ MnO 4 - + Cl - (c) Cl2O1g2 + NH 31g2 ¡

solution.

(b) Fe1OH231s2 + OCl - ¡ FeO 4 2- + Cl - N21g2 + NH 4Cl1s2 + H 2O1l2

(d) Ag1s2 + CrO 4 2- : Ag + + Cr1OH231s2

(c) ClO2 ¡ ClO 3 - + Cl - 46. The following reactions do not occur in aqueous solu-
tions. Balance their equations by the half-equation

(a) CH 41g2 + NH 31g2 + O 21g2 ¡

40. Balance these equations for redox reactions occurring method, as suggested in Are You Wondering 5-2.

(a) CrO 4 2- + S 2O 4 2- ¡ Cr1OH231s2 + SO 3 2-

in basic solution.

(b) 3Fe1CN2643- + N2H 4 ¡ [Fe1CN26]4- + N21g2 (b) NO1g2 + H 21g2 ¡ NH 31g2 + H 2O1g2
HCN1g2 + H 2O1g2

(c) Fe1s2 + H 2O1l2 + O 21g2 ¡ Fe1OH231s2

186 Chapter 5 Introduction to Reactions in Aqueous Solutions

Oxidizing and Reducing Agents

47. What are the oxidizing and reducing agents in the fol- strength of the oxidizing agent and other conditions.
lowing redox reactions? By adding H +, H 2O, and/or OH - as necessary, write
(a) 5 SO 3 2- + 2 MnO 4 - + 6 H + ¡ redox equations to show the oxidation of S 2O 3 2- to

(b) 2 NO 21g2 + 7 H 21g2 ¡ 2 NH 31g2 + 4 H 2O1g2

5 SO 4 2- + 2 Mn2+ + 3 H 2O (a) S 4O 6 2- by I 2 (iodide ion is another product)

(c) 2 3Fe1CN2644- + H 2O2 + 2 H + ¡

(b) HSO 4 - by Cl2 (chloride ion is another product)

2 3Fe1CN2643- + 2 H 2O
(c) SO 4 2- by OCl - in basic solution (chloride ion is
another product)
2-
48. Thiosulfate ion, S 2O 3 , is a reducing agent that can
be oxidized to different products, depending on the

Neutralization and Acid Base Titrations

49. What volume of 0.0962 M NaOH is required to exactly (b) A 25.00 mL sample of the approximately 0.10 M
neutralize 10.00 mL of 0.128 M HCl? HCl prepared in part (a) requires 20.93 mL of 0.1186 M

H 2SO 41aq2 requires 23.31 mL of NaOH. What must

50. The exact neutralization of 10.00 mL of 0.1012 M NaOH for its titration. What is the molarity of the
HCl(aq)?

H 2SO 41aq2 + 2 NaOH1aq2 ¡

be the molarity of the NaOH(aq)? (c) Why is a titration necessary? That is, why not pre-

Na 2SO41aq2 + 2 H 2O1l2
pare a standard solution of 0.1000 M HCl simply by
an appropriate dilution of the concentrated HCl(aq)?
57. A 25.00 mL sample of 0.132 M HNO3 is mixed with
51. How many milliliters of 2.155 M KOH are required to 10.00 mL of 0.318 M KOH. Is the resulting solution

A 7.55 g sample of Na2CO31s2 is added to 125 mL of a

titrate 25.00 mL of 0.3057 M CH3CH2COOH (propi- acidic, basic, or exactly neutralized?
onic acid)? 58.
52. How many milliliters of 0.0844 M Ba1OH22 are vinegar that is 0.762 M CH3COOH. Will the resulting
required to titrate 50.00 mL of 0.0526 M HNO3 ? solution still be acidic? Explain.
53. An NaOH(aq) solution cannot be made up to an exact 59. Refer to Example 5-9. Suppose the analysis of all vine-
concentration simply by weighing out the required gar samples uses 5.00 mL of the vinegar and 0.1000 M
mass of NaOH, because the NaOH is not pure. Also, NaOH for the titration. What volume of the 0.1000 M
water vapor condenses on the solid as it is being NaOH would represent the legal minimum 4.0%, by
weighed. The solution must be standardized by titra- mass, acetic acid content of the vinegar? That is,
tion. For this purpose, a 25.00 mL sample of an calculate the volume of 0.1000 M NaOH so that if a
NaOH(aq) solution requires 28.34 mL of 0.1085 M titration requires more than this volume, the legal
HCl. What is the molarity of the NaOH(aq)? minimum limit is met (less than this volume, and the
HCl1aq2 + NaOH1aq2 ¡ NaCl1aq2 + H 2O1l2 limit is not met).

for other cleaning purposes, is NH 31aq2. The NH 3

60. The electrolyte in a lead storage battery must have a
54. Household ammonia, used as a window cleaner and
concentration between 4.8 and 5.3 M H2SO4 if the bat-
tery is to be most effective. A 5.00 mL sample of a bat-
present in a 5.00 mL sample is neutralized by 28.72 mL
tery acid requires 49.74 mL of 0.935 M NaOH for its
of 1.021 M HCl. The net ionic equation for the neutral-
complete reaction (neutralization). Does the concentra-

NH 31aq2 + H +1aq2 ¡ NH 4 +1aq2

ization is
tion of the battery acid fall within the desired range?
[Hint: Keep in mind that the H2SO4 produces two H+
What is the molarity of NH 3 in the sample? ions per formula unit.]
55. We want to determine the acetylsalicyclic acid content 61. Which of the following points in a titration is repre-
of a series of aspirin tablets by titration with NaOH(aq). sented by the molecular view shown in the sketch?
Each of the tablets is expected to contain about 0.32 g of (a) 20% of the necessary titrant added in the titration
HC9H 7O4. What molarity of NaOH(aq) should we use of NH4Cl1aq2 with HCl(aq)
for titration volumes of about 23 mL? (This procedure
ensures good precision and allows the titration of two

HC9H 7O41aq2 + OH -1aq2 ¡

samples with the contents of a 50 mL buret.)

C9H 7O 4 -1aq2 + H 2O1l2

56. For use in titrations, we want to prepare 20 L of
HCl(aq) with a concentration known to four signifi-
cant figures. This is a two-step procedure beginning
with the preparation of a solution of about 0.10 M
HCl. A sample of this dilute HCl(aq) is titrated with a
NaOH(aq) solution of known concentration.

1d = 1.19 g>mL; 38% HCl, by mass2 must be diluted

(a) How many milliliters of concentrated HCl1aq2

with water to 20.0 L to prepare 0.10 M HCl?

 Integrative and Advanced Exercises 187

of NH31aq2 with HCl(aq)

(b) 20% of the necessary titrant added in the titration 62. Using the sketch in Exercise 61 as a guide, sketch the

(c) the equivalence point in the titration of NH31aq2

molecular view of a solution in which
(a) HCl(aq) is titrated to the equivalence point with
with HCl(aq) KOH(aq)

of NH31aq2 with HCl(aq)

(d) 120% of the necessary titrant added in the titration (b) CH3COOH1aq2 is titrated halfway to the equiva-
lence point with NaOH(aq).

Stoichiometry of Oxidation Reduction Reactions

63. A KMnO41aq2 solution is to be standardized by titra- 66. The concentration of Mn2+1aq2 can be determined by
tion against As2O31s2. A 0.1078 g sample of As2O3 titration with MnO 4 - 1aq2 in basic solution. A 25.00
requires 22.15 mL of the KMnO41aq2 for its titration. mL sample of Mn2+ 1aq2 requires 37.21 mL of
What is the molarity of the KMnO41aq2? 0.04162 M KMnO4 for its titration. What is 3Mn2+ 4 in

Mn2+ + MnO 4 - ¡ MnO21s2 1not balanced2

5 As2O3 + 4 MnO 4 - + 9 H 2O + 12 H + ¡ the sample?
10 H3AsO4 + 4 Mn2+
64. Refer to Example 5-6. Assume that the only reducing 67. The titration of 5.00 mL of a saturated solution of
agent present in a particular wastewater is SO 3 2-. If a sodium oxalate, Na2C2O4, at 25 °C requires 25.8 mL
25.00 mL sample of this wastewater requires 31.46 mL of 0.02140 M KMnO4 in acidic solution. What mass of
of 0.02237 M KMnO4 for its titration, what is the Na2C2O4 in grams would be present in 1.00 L of this
molarity of SO 3 2- in the wastewater? saturated solution?

HCl(aq), and the iron is obtained as Fe2+1aq2. This

Mn2+ + CO21g2 1not balanced2
65. An iron ore sample weighing 0.9132 g is dissolved in
C2O 4 2- + MnO 4 - ¡
solution is then titrated with 28.72 mL of 0.05051 M
K2Cr2O7. What is the mass percent Fe in the ore 68. Refer to the Integrative Example. In the treatment of

CrO 4 2-, how many grams of (a) Cr1OH231s2 would

sample? 1.00 * 102 L of a wastewater solution that is 0.0126 M
6 Fe 2+ + 14 H + + Cr2O 7 2- ¡
6 Fe3+ + 2 Cr3+ + 7 H2O precipitate; (b) Na2S2O4 would be consumed?

Integrative and Advanced Exercises

69. Write net ionic equations for the reactions depicted in (d) preparation of chlorous acid: an aqueous suspen-

H2SO41aq2
photo (a) sodium metal reacts with water to produce sion of solid barium chlorite is treated with dilute

When concentrated CaCl21aq2 is added to

hydrogen; photo (b) an excess of aqueous iron(III) chlo-

Na2HPO41aq2, a white precipitate forms that is 38.7%

ride is added to the solution in (a); and photo (c) the 71.
precipitate from (b) is collected and treated with an
excess of HCl(aq). Ca by mass. Write a net ionic equation representing
the probable reaction that occurs.
72. You have a solution that is 0.0250 M Ba1OH22 and the
following pieces of equipment: 1.00, 5.00, 10.00, 25.00,
and 50.00 mL pipets and 100.0, 250.0, 500.0, and 1000.0

this equipment to produce a solution in which 3OH-4

mL volumetric flasks. Describe how you would use

is 0.0100 M.
73. Sodium hydroxide used to make standard NaOH(aq)
solutions for acid base titrations is invariably contam-
inated with some sodium carbonate. (a) Explain why,
except in the most precise work, the presence of this
sodium carbonate generally does not seriously affect
(a) (b) (c) the results obtained, for example, when NaOH(aq) is
used to titrate HCl(aq). (b) Conversely, show that if
70. Following are some laboratory methods occasionally Na2CO3 comprises more than 1% to 2% of the solute in
used for the preparation of small quantities of chemi- NaOH(aq), the titration results are affected.
cals. Write a balanced equation for each. 74. A 110.520 g sample of mineral water is analyzed for its
(a) preparation of H2S1g2: HCl(aq) is heated with magnesium content. The Mg2+ in the sample is first

(b) preparation of Cl21g2: HCl(aq) is heated with

FeS(s) precipitated as MgNH4PO4, and this precipitate is

MnO21s2; MnCl21aq2 and H2O1l2 are other products

then converted to Mg2P2O7, which is found to weigh
0.0549 g. Express the quantity of magnesium in the
(c) preparation of N2: Br2 and NH3 react in aqueous sample in parts per million (that is, in grams of Mg
solution; NH4Br is another product per million grams of H2O).
188 Chapter 5 Introduction to Reactions in Aqueous Solutions

75. What volume of 0.248 M CaCl2 must be added to leaching of H+ ions causes the water to become very

surface water, limestone 1CaCO32 is added to the tail-

335 mL of 0.186 M KCl to produce a solution with a acidic. To prevent acidification of nearby ground or
concentration of 0.250 M Cl-? Assume that the solu-

CaCO31s2 + 2 H +1aq2 ¡
tion volumes are additive. ings to neutralize the H+ ions:

Ca2+1aq2 + H2O1l2 + CO21g2

76. An unknown white solid consists of two compounds,
each containing a different cation. As suggested in the
illustration, the unknown is partially soluble in water.

and O2. [Hint: Start with the half-equations FeS 21s2 :

The solution is treated with NaOH(aq) and yields a (a) Balance the equation above for the reaction of FeS2

Fe 3+1aq2 + SO 4 2-1aq2 and O21g2 : H 2O1l2.]

white precipitate. The part of the original solid that is

(b) What is the minimum amount of CaCO31s2

insoluble in water dissolves in HCl(aq) with the evo-

with 1NH422SO41aq2 and yields a white precipitate.

lution of a gas. The resulting solution is then treated
required, per kilogram of tailings, to prevent con-
(a) Is it possible that any of the cations Mg2+, Cu2+, tamination if the tailings contain 3% S by mass? Assume
Ba2+, Na+, or NH4+ were present in the original that all the sulfur in the tailings is in the form FeS2.
unknown? Explain your reasoning. (b) What com- 81. A sample of battery acid is to be analyzed for its sul-
pounds could be in the unknown mixture (that is, furic acid content. A 1.00 mL sample weighs 1.239 g.
what anions might be present)? This 1.00 mL sample is diluted to 250.0 mL, and
10.00 mL of this diluted acid requires 32.44 mL of
Solution 0.00498 M Ba1OH22 for its titration. What is the mass
* percent of H2SO4 in the battery acid? (Assume that
KOH(aq) white ppt complete ionization and neutralization of the H2SO4
occurs.)
82. A piece of marble (assume it is pure CaCO3 ) reacts
with 2.00 L of 2.52 M HCl. After dissolution of the
Solid marble, a 10.00 mL sample of the resulting solution is
* withdrawn, added to some water, and titrated with
HCl(aq) solution + gas 24.87 mL of 0.9987 M NaOH. What must have been
* the mass of the piece of marble? Comment on the pre-
(NH4)2SO4(aq) white ppt cision of this method; that is, how many significant
figures are justified in the result?

method of preparing small quantities of Cl21g2. If a

77. Balance these equations for reactions in acidic solution. 83. The reaction below can be used as a laboratory
(a) IBr + BrO 3 - + H + ¡ IO 3 - + Br - + H 2O
(b) C2H 5NO3 + Sn ¡ 62.6 g sample that is 98.5% K2Cr2O7 by mass is
NH2OH + CH3CH2OH + Sn2+ allowed to react with 325 mL of HCl(aq) with a den-

grams of Cl21g2 are produced?

- sity of 1.15 g>mL and 30.1% HCl by mass, how many
(c) As2S 3 + NO 3 ¡ H 3AsO4 + S + NO
(d) H 5IO 6 + I 2 ¡ IO 3 - + H + + H 2O

Cr3+ + H2O + Cl21g2 1not balanced2

(e) S2F2 + H2O ¡ S8 + H2S4O6 + HF Cr2O 7 2- + H + + Cl - ¡
78. Balance these equations for reactions in basic solution.

84. Refer to Example 5-10. Suppose that the KMnO41aq2

(a) Fe2S 3 + H 2O + O2 ¡ Fe1OH23 + S
(b) O 2 - + H 2O ¡ OH - + O 2
(c) CrI 3 + H 2O2 ¡ CrO 4 2- + IO 4 - were standardized by reaction with As2O3 instead of

3Ag1CN224- + H 2O
(d) Ag + CN- + O2 + OH- ¡ iron wire. If a 0.1304 g sample that is 99.96% As2O3 by

liters of the KMnO41aq2 would have been required?

mass had been used in the titration, how many milli-
(e) B2Cl4 + OH ¡ BO 2 + Cl - + H 2O + H 2
- -

H3AsO4 + Mn2+ 1not balanced2

79. A method of producing phosphine, PH3, from ele- As2O3 + MnO 4 - + H + + H 2O ¡
mental phosphorus, P4, involves heating the P4 with
H2O. An additional product is phosphoric acid,
H3PO4. Write a balanced equation for this reaction. 85. A new method under development for water treatment

of producing ClO2 involves passing Cl21g2 into a con-

80. Iron (Fe) is obtained from rock that is extracted from uses chlorine dioxide rather than chlorine. One method

centrated solution of sodium chlorite. Cl21g2 and

open pit mines and then crushed. The process used to
obtain the pure metal from the crushed rock produces

and ClO21g2 are the sole products. If the reaction has a

solid waste, called tailings, which are stored in dis- sodium chlorite are the sole reactants, and NaCl1aq2
posal areas near the mines. The tailings pose a serious

as pyrite 1FeS22, which oxidize in air to produce metal 2.0 M NaClO21aq2 treated in this way?
environmental risk because they contain sulfides, such 97% yield, what mass of ClO2 is produced per gallon of

ions and H+ ions that can enter into surface water or 86. The active component in one type of calcium dietary
ground water. The oxidation of FeS2 to Fe3+ is supplement is calcium carbonate. A 1.2450 g tablet of

FeS 21s2 + O21g2 + H 2O1l2 ¡

described by the unbalanced chemical equation below. the supplement is added to 50.00 mL of 0.5000 M HCl

Fe 3+1aq2 + SO 4 2-1aq2 + H +1aq2 1not balanced2

and allowed to react. After completion of the reaction,
the excess HCl(aq) requires 40.20 mL of 0.2184 M
NaOH for its titration to the equivalence point. What
Thus, the oxidation of pyrite produces Fe3 + and H+ is the calcium content of the tablet, expressed in mil-
ions that can leach into surface or ground water. The ligrams of Ca2+?
 Feature Problems 189

87. A 0.4324 g sample of a potassium hydroxide lithium 91. Warfarin, C19H16O4, is the active ingredient used in
hydroxide mixture requires 28.28 mL of 0.3520 M HCl some anticoagulant medications. The amount of
for its titration to the equivalence point. What is the warfarin in a particular sample was determined as
mass percent lithium hydroxide in this mixture? follows. A 13.96 g sample was first treated with an
88. Chile saltpeter is a natural source of NaNO3; it also alkaline I2 solution to convert C19H16O4 to CHI3. This
contains NaIO3. The NaIO3 can be used as a source of treatment gives one mole of CHI3 for every mole of
iodine. Iodine is produced from sodium iodate in a C19H16O4 that was initially present in the sample. The

IO3 -1aq2 + HSO3 -1aq2 ¡ ment with excess AgNO31aq2:

two-step process occurring under acidic conditions: iodine in CHI3 is then precipitated as AgI(s) by treat-

I -1aq2 + SO4 2-1aq2 1not balanced2 CHI 31aq2 + 3 AgNO31aq2 + H 2O1l2 ¡

I 1aq2 + IO3 1aq2 ¡ 3 AgI1s2 + 3 HNO31aq2 + CO1g2
I21s2 + H2O1l2 1not balanced2
- -

In the illustration, a 5.00 L sample of a NaIO31aq2

If 0.1386 g solid AgI were obtained, then what is the per-

solution containing 5.80 g NaIO3>L is treated with the

centage by mass of warfarin in the sample analyzed?
92. Copper refining traditionally involves roasting insol-

process produces large quantities of SO21g2, which is a

stoichiometric quantity of NaHSO3 (no excess of uble sulfide ores (CuS) with oxygen. Unfortunately, the

NaIO31aq2 is added to the reaction mixture to bring

either reactant). Then, a further quantity of the initial
major contributor to pollution and acid rain. An alter-

HNO31aq2, which dissolves the CuS without generat-

about the second reaction. (a) How many grams of native process involves treating the sulfide ore with
NaHSO3 are required in the first step? (b) What addi-
tional volume of the starting solution must be added ing any SO2. The unbalanced chemical equation for the

CuS1s2 + NO 3 - 1aq2 ¡
in the second step? reaction is given below.

Cu2+ 1aq2 + NO1g2 + HSO 4 -1aq2 1not balanced2

5.80 g NaIO3/L
(a) ? g NaHSO3
What volume of concentrated nitric acid solution is
required per kilogram of CuS? Assume that the con-
centrated nitric acid solution is 70% HNO3 by mass
and has a density of 1.40 g/mL.
5.00 L 93. Phosphorus is essential for plant growth, but an
excess of phosphorus can be catastrophic in aqueous
ecosystems. Too much phosphorus can cause algae to
(b) ? L grow at an explosive rate and this robs the rest of the
ecosystem of oxygen. Effluent from sewage treatment
89. The active ingredients in a particular antacid tablet plants must be treated before it can be released into
are aluminum hydroxide, Al1OH23, and magnesium lakes or streams because the effluent contains signifi-
hydroxide, Mg1OH22. A 5.00 * 102 mg sample of cant amounts of H 2PO 4 - and HPO 4 2-. (Detergents
the active ingredients was dissolved in 50.0 mL of are a major contributor to phosphorus levels in
0.500 M HCl. The resulting solution, which was still domestic sewage because many detergents contain
acidic, required 16.5 mL of 0.377 M NaOH for neutral- Na2HPO4.) A simple way to remove H 2PO 4 - and
ization. What are the mass percentages of Al1OH23 HPO 4 2- from the effluent is to treat it with lime, CaO,
and Mg1OH22 in the sample? which produces Ca2+ and OH- ions in water. The
OH- ions convert H 2PO 4 - and HPO 4 2- ions into

combine to form a precipitate of Ca51PO423OH1s2.

90. A compound contains only Fe and O. A 0.2729 g sam-
ple of the compound was dissolved in 50 mL of con- PO 4 3- ions and, finally, Ca2+ , OH-, and PO 4 3- ions
centrated acid solution, reducing all the iron to Fe2+
ions. The resulting solution was diluted to 100 mL and (a) Write balanced chemical equations for the four reac-
then titrated with a 0.01621 M KMnO4 solution. The tions described above.
unbalanced chemical equation for reaction between [Hint: The reactants are CaO and H 2O; H 2PO 4 - and
OH -; HPO 4 2- and OH -; Ca2+ , PO 4 3-, and OH-.]
MnO 4 -1aq2 + Fe 2+1aq2 ¡
Fe2+ and MnO 4 - is given below.

Mn2+1aq2 + Fe3+1aq2 1not balanced2

(b) How many kilograms of lime are required to
remove the phosphorus from a 1.00 * 104 L holding
tank filled with contaminated water, if the water con-
The titration required 42.17 mL of the KMnO4 solution tains 10.0 mg of phosphorus per liter?
to reach the pink endpoint. What is the empirical for-
mula of the compound?

Feature Problems
preparation. The THF is present as NaC5H 5 # 1THF2x,
94. Sodium cyclopentadienide, NaC5H 5, is a common tetrahydrofuran (THF), C4H8O, a solvent used in its
reducing agent in the chemical laboratory, but there is a
problem in using it: NaC5H 5 is contaminated with and it is generally necessary to know exactly how
190 Chapter 5 Introduction to Reactions in Aqueous Solutions

much of this NaC5H 5 # 1THF2x is present. This is the dilute H2SO41aq2 requires 22.24 mL of 0.4498 M

NaC5H 5 # 1THF2x to react with water,

accomplished by allowing a small amount of the NaOH for its titration. What is the percent protein in

NaC5H 5 # 1C4H 8O2x + H 2O ¡

the meat?
97. Blood alcohol content (BAC) is often reported in
weight volume percent (w/v%). For example, a BAC
NaOH1aq2 + C5H 5 ¬ H + x C4H 8O
of 0.10% corresponds to 0.10 g CH3CH2OH per 100
followed by titration of the NaOH(aq) with a standard mL of blood. Estimates of BAC can be obtained from

the value of x in the formula NaC5H 5 # 1THF2x.

acid. From the sample data tabulated below, determine breath samples by using a number of commercially
available instruments, including the Breathalyzer for
which a patent was issued to R. F. Borkenstein in
1958. The chemistry behind the Breathalyzer is

Mass of NaC5H 5 # 1THF2x

Trial 1 Trial 2
described by the oxidation reduction reaction below,

CH3CH2OH1g2 + Cr2O7 2-1aq2 ¡

0.242 g 0.199 g which occurs in acidic solution:
Volume of 0.1001 M HCl
1yellow-orange2
required to titrate NaOH(aq) 14.92 mL 11.99 mL

CH3COOH1aq2 + Cr3+1aq2 1not balanced2

ethyl alcohol

1green2
95. Manganese is derived from pyrolusite ore, an
impure manganese dioxide. In the procedure used to
analyze a pyrolusite ore for its MnO2 content, a 0.533 g

1H2C2O4 # 2 H2O2 in an acidic medium. Following

A Breathalyzer instrument contains two ampules, each

of 9 mol>L H2SO41aq2. One of the ampules is used as

sample is treated with 1.651 g oxalic acid
of which contains 0.75 mg K2Cr2O7 dissolved in 3 mL
this reaction, the excess oxalic acid is titrated with
0.1000 M KMnO4, 30.06 mL being required. What is reference. When a person exhales into the tube of the
the mass percent MnO2 in the ore? Breathalyzer, the breath is directed into one of the

Mn2+ + H2O + CO2 1not balanced2

ampules, and ethyl alcohol in the breath converts
H2C2O4 + MnO2 + H+ ¡ Cr2O 7 2- into Cr3+. The instrument compares the colors
of the solutions in the two ampules to determine the

Mn2+ + H2O + CO2 1not balanced2

H 2C2O4 + MnO 4 - + H + ¡ breath alcohol content (BrAC), and then converts this
into an estimate of BAC. The conversion of BrAC into
96. The Kjeldahl method is used in agricultural chem- BAC rests on the assumption that 2100 mL of air
istry to determine the percent protein in natural exhaled from the lungs contains the same amount of
products. The method is based on converting all the alcohol as 1 mL of blood. With the theory and assump-
protein nitrogen to ammonia and then determining tions described in this problem, calculate the molarity
the amount of ammonia by titration. The percent of K2Cr2O7 in the ampules before and after a breath
nitrogen in the sample under analysis can be calcu- test in which a person with a BAC of 0.05% exhales
lated from the quantity of ammonia produced. 0.500 L of his breath into a Breathalyzer instrument.
Interestingly, the majority of protein molecules in 98. In this problem, we describe an alternative method
living matter contain just about 16% nitrogen. for balancing equations for oxidation-reduction reac-
A 1.250 g sample of meat is heated with concen- tions. The method is similar to the method given pre-

nitrogen in the meat to 1NH422SO4. Then excess

trated sulfuric acid and a catalyst to convert all the viously in Tables 5.5 and 5.6, but it places more
emphasis on the assignment of oxidation states. (The

to expel NH31g2. All the nitrogen from the sample is

NaOH(aq) is added to the mixture, which is heated method summarized in Tables 5.5 and 5.6 does not

found in the NH31g2, which is then absorbed in

require you to assign oxidation states.) An emphasis

and neutralized by 50.00 mL of dilute H2SO41aq2.

on oxidation states is warranted because oxidation

The excess H2SO41aq2 requires 32.24 mL of 0.4498 M

states are useful not only for keeping track of elec-
trons but also for predicting chemical properties. The
NaOH for its titration. A separate 25.00 mL sample of method is summarized in the table below.

A Method for Balancing Equations for Oxidation Reduction Reactions

That Occur in an Acidic or a Basic Aqueous Solution
1. Assign oxidation states to each element in the reaction and identify the species being oxidized and reduced.
2. Write separate, unbalanced equations for the oxidation and reduction half-reactions.
3. Balance the separate half-equations, in this order:
first with respect to the element being oxidized or reduced
then by adding electrons to one side or the other to account for the number of electrons produced
(oxidation) or consumed (reduction)
4. Combine the half-reactions algebraically so that the total number of electrons cancels out.
5. Balance the net charge by either adding OH - (for basic solutions) or H + (for acidic solutions).
6. Balance the O and H atoms by adding H 2O.
7. Check that the final equation is balanced with respect to each type of atom and with respect to charge.
 Self-Assessment Exercises 191

The method offers a couple of advantages. First, the rately and must balance twice for charge and twice for
method applies to both acidic and basic environments hydrogen and oxygen.
because we balance charges by using either H+ (for Use the alternative method described above to bal-

(a) Cr2O7 2- 1aq2 + Cl -1aq2 ¡

acidic environments) or OH- (for basic environments). ance the following oxidation-reduction equations.

Cr3+1aq2 + Cl21g2 1acidic solution2

Second, the method is somewhat more efficient than

(b) C2O4 1aq2 + MnO4 -1aq2 ¡

the method we described previously because, in the
method described here, we balance only once for

CO3 2-1aq2 + MnO21s2 1basic solution2

2-
charge and only once for hydrogen and oxygen. In the
other method, we focus on the half-equations sepa-

Self-Assessment Exercises
(b) 3 4; (c) spectator ion; (d) weak
? Fe2+1aq2 + O21g2 + 4 H+1aq2 ¡
99. In your own words, define or explain the terms or 110. In the equation

? Fe3+1aq2 + 2 H2O1l2
symbols (a)
acid.
100. Briefly describe (a) half-equation method of balanc-
ing redox equations; (b) disproportionation reaction; the missing coefficients (a) are each 2; (b) are each 4;
(c) titration; (d) standardization of a solution. (c) can have any values as long as they are the same;
101. Explain the important distinctions between (a) a (d) must be determined by experiment.
strong electrolyte and strong acid; (b) an oxidizing 111. What is the simplest ratio a:b when the equation

a ClO -1aq2 + b I 1aq2 c Cl -1aq2 + d IO -1aq2

agent and reducing agent; (c) precipitation reactions below is properly balanced?
and neutralization reactions; (d) half-reaction and acidic "
overall reaction. 2 solution 3

102. The number of moles of hydroxide ion in 0.300 L of (a) 2:5; (b) 5:2; (c) 1:5; (d) 5:1; (e) 2:3.
0.0050 M Ba1OH22 is (a) 0.0015; (b) 0.0030; (c) 0.0050; 112. In the half-reaction in which NpO 2 + is converted to

103. The highest 3H+4 will be found in an aqueous solu-

(d) 0.010. Np4+, the number of electrons appearing in the half-
equation is (a) 1; (b) 2; (c) 3; (d) 4.
tion that is (a) 0.10 M HCl; (b) 0.10 M NH3; (c) 0.15 M 113. Classify each of the following statements as true or

104. To precipitate Zn2+ from Zn1NO3221aq2, add

CH3COOH; (d) 0.10 M H2SO4. false.

(a) NH4Cl; (b) MgBr2; (c) K2CO3; (d) 1NH422SO4.

(a) Barium chloride, BaCl2, is a weak electrolyte in

(b) In the reaction H -1aq2 + H 2O1l2 : H 21g2 +

aqueous solution.

OH-1aq2, water acts as both an acid and an oxidiz-

105. When treated with dilute HCl(aq), the solid that
reacts to produce a gas is (a) BaSO3; (b) ZnO;
(c) NaBr; (d) Na2SO4. ing agent.

bonate, Na2CO31aq2, is treated with excess aqueous

106. What is the net ionic equation for the reaction that (c) A precipitate forms when aqueous sodium car-

an aqueous solution of Pb1NO322?

occurs when an aqueous solution of KI is added to
hydrochloric acid, HCl(aq).
107. When aqueous sodium carbonate, Na2CO3, is (d) Hydrofluoric acid, HF, is a strong acid in water.

0.010 M solution of Mg1NO322 is a better conductor

treated with dilute hydrochloric acid, HCl, the prod- (e) Compared with a 0.010 M solution of NaNO3, a
ucts are sodium chloride, water, and carbon dioxide
gas. What is the net ionic equation for this reaction? of electricity.
108. Describe the synthesis of each of the following ionic 114. Which of the following reactions are oxidation

(a) H 2CO 31aq2 ¡ H 2O1l2 + CO21g2

compounds, starting from solutions of sodium and reduction reactions?

(b) 2 Li1s2 + 2 H 2O1l2 ¡ 2 LiOH1aq2 + H 21g2

nitrate salts. Then write the net ionic equation for

(a) Zn31PO422; (c) 4 Ag1s2 + PtCl41aq2 ¡ 4 AgCl1s2 + Pt1s2

each synthesis.

(d) 2 HClO41aq2 + Ca1OH221aq2 ¡

2 H2O1l2 + Ca1ClO4221aq2
(b) Cu1OH22;
(c) NiCO3.

4 NO1g2 + 3 O21g2 + 2 H 2O1l2 ¡

109. Consider the following redox reaction: 115. Similar to Figure 5-4(c), but using the formulas

4 NO 3 -1aq2 + 4 H +1aq2
HAc, Ac-, and H3O+, give a more accurate represen-
tation of CH3COOH1aq2 in which ionization is 5%
complete.
(a) Which species is oxidized? 116. Appendix E describes a useful study aid known as
(b) Which species is reduced? concept mapping. Using the method presented in
(c) Which species is the oxidizing agent? Appendix E, construct a concept map illustrating
(d) Which species is the reducing agent? the different concepts introduced in Sections 5-4, 5-5,
(e) Which species gains electrons? and 5-6.
(f) Which species loses electrons?