Ch04 Lecture

Chapter 4
Reactions in
Aqueous Solution
© 2022 Pearson Education Ltd.

Solutions
• Solutions are defined as homogeneous mixtures of
two or more pure substances.
• The solvent is present in greatest abundance.
• All other substances are solutes.
• When water is the solvent, the solution is called an
aqueous solution.

Chemical Reactions:

Electrolytes and Nonelectrolytes
• An electrolyte is a substance that dissociates into
ions when dissolved in water.
• A nonelectrolyte may dissolve in water, but it does
not dissociate into ions when it does so.
Figure 4.1 Completion of an electrical circuit with an electrolyte turns on the light.
Aqueous Solutions
• Substances can dissolve in water by different ways:
– Ionic compounds dissolve by dissociation, where
water surrounds the separated ions.
– Molecular compounds interact with water, but most
do NOT dissociate.
– Some molecular substances react with water when
they dissolve.
• All substances dissolve by solvation, surrounding of the
solute by solvent.

Aqueous Solutions
Figure 4.2 Dissolution in water.

(a) When an ionic compound, such as sodium chloride, NaCl,
dissolves in water, H2O molecules separate, surround, and
uniformly disperse the ions into the liquid.
(b) Molecular substances that dissolve in water, such as
methanol, CH3OH, usually do so without forming ions.
Reaction in Aqueous Solutions
• Aqueous solution ( 水溶液 )
Water as solvent ( 溶劑 ): A polar molecule
δ
－ δ － partial negative charge
δ+ partial negative charge
δ+ δ+

Hydration ( 水合 )
When ionic compound (NaCl) dissolved in water
The ions are solvated
NaCl(s) → Na+(aq) + Cl － (aq)

Water as solvent: hydration
Does not dissolve nonpolar substances, dissolves polar substances

The nature of aqueous solution
Solute ( 溶質 ) in aqueous solution:
強電解質 (Strong electrolyte): complete dissociation
Soluble salts ( 可溶鹽類 , NaCl)
Strong acids ( 強酸 , HCl)
Strong bases ( 強鹼 , NaOH)
弱電解質 ( Weak electrolyte):
Weak acids ( 弱酸 , CH3COOH, ~ 1%
ionized)
Weak bases( 弱鹼 , NH3 氨 )
非電解質 (nonelectrolyte)
任何溶於水，卻不產生任何離子的物質
( 乙醇、糖 … .)
Electrolytes
• A strong electrolyte dissociates completely when
dissolved in water.
• A weak electrolyte only dissociates partially when
dissolved in water.
• A nonelectrolyte does NOT dissociate in water.

Strong vs. Weak Electrolytes—Equilibrium
• A strong electrolyte dissociates completely when
dissolved in water. Its equations for the reaction of its
dissociation look familiar:
– HCl (aq) H+ (aq) + Cl– (aq)
• A weak electrolyte only dissociates partially when
dissolved in water. Its equations indicate a chemical
equilibrium, where a reaction goes both forward and
backward:
– CH3COOH (aq) H+ (aq) + CH3COO– (aq)

Sample Exercise 4.1 Relating Relative Numbers of Anions
and Cations to Chemical
Formulas
The accompanying diagram represents an aqueous solution of either MgCl 2, KCl, or K2SO4. Which solution does the
drawing best represent?
Solution
Analyze We are asked to associate the charged spheres in the
diagram with ions present in a solution of an ionic substance.
Plan We examine each ionic substance given to determine the

relative numbers and charges of its ions. We then correlate these
ionic species with the ones shown in the diagram.
Solve The diagram shows twice as many cations as anions,

consistent with the formulation K2SO4.
Check Notice that the net charge in the diagram is zero, as it must
be if it is to represent an ionic substance.

Sample Exercise 4.1 Relating Relative Numbers of
Anions and Cations to
Continued
Chemical Formulas
Practice Exercise
If you were to draw diagrams representing aqueous solutions of (a) NiSO4, (b) Ca(NO3)2, (c) Na3PO4,
(d) Al2(SO4)3, how many anions would you show if each diagram contained six cations?

Precipitation Reactions
• Precipitation reactions occur when two solutions
containing soluble salts are mixed and an insoluble
salt is produced.
• The solid is called a precipitate.

Precipitation Reactions
Figure 4.3 A precipitation reaction.

Solubility of Ionic Compounds
• Not all ionic compounds dissolve in water.
• A list of solubility rules is used to decide what
combination of ions will dissolve.

Reaction in Which a Solid Forms
Using Solubility Rules

1. NO3 － Salts → soluble ( 可溶 )
2. Na+, K+, NH4+ Salts → soluble
3. Cl － Salts → soluble, except ( 例外 ) AgCl, PbCl2 ( 可溶於
熱水 ), Hg2Cl2
4. SO4 － Salts → soluble, except BaSO4, PbSO4 , CaSO4
5. OH － Salts → slightly soluble ( 微溶 ) except NaOH, KOH,
Ba(OH)2 , Ca(OH)2
Solubility: NaOH KOH >> Ba(OH)2 , Ca(OH)2 >> other
OH － Salt
6. S2 － CO3 － PO4 － Salts → slightly soluble ( 微溶 )
How to Predict Precipitates When Solutions of Two Ionic Compounds Are Mixed

How to Predict Whether a Precipitate Forms
When Strong Electrolytes are Mixed
1) Note the ions present in the reactants.
2) Consider the possible cation-anion combinations.
3) Use Table 4.1 to determine if any of the
combinations is insoluble.

Sample Exercise 4.2 Using Solubility Rules
Classify these ionic compounds as soluble or insoluble in water: (a) sodium carbonate, Na2CO3, (b) lead
sulfate, PbSO4.
Solution
Analyze We are given the names and formulas of two ionic compounds and asked to predict whether they are soluble
or insoluble in water.
Plan We can use Table 4.1 to answer the question. Thus, we need to focus on the anion in each compound because the
table is organized by anions.
Solve
(a) According to Table 4.1, most carbonates
are insoluble. But carbonates of the alkali
metal cations (such as sodium ion) are an
exception to this rule and are soluble.
Thus, Na2CO3 is soluble in water.
(b) Table 4.1 indicates that although most

sulfates are water soluble, the sulfate of
Pb2+ is an exception. Thus, PbSO4 is insoluble in water.

Sample Exercise 4.2 Using Solubility Rules
Continued
Practice Exercise
Which of the following compounds is insoluble in water?
(a) (NH4)2S (b) CaCO3 (c) NaOH (d) Ag2SO4 (e) Pb(CH3COO)2

Exchange (Metathesis) Reactions
• Metathesis comes from a Greek word that means “to
transpose.”
• It appears as though the ions in the reactant
compounds exchange, or transpose, ions, as seen in
the given equation.

Completing and Balancing
Metathesis Equations
• Steps to follow:
1) Use the chemical formulas of the reactants to
determine which ions are present.
2) Write formulas for the products: cation from one
reactant, anion from the other. Use charges to
write proper subscripts.
3) Check your solubility rules. If either product is
insoluble, a precipitate forms.
4) Balance the equation.

Sample Exercise 4.3 Predicting a Metathesis Reaction
(a) Predict the identity of the precipitate that forms when aqueous solutions of BaCl 2 and K2SO4
are mixed. (b) Write the balanced chemical equation for the reaction.
Solution
Analyze We are given two ionic reactants and asked to predict the insoluble product that they form.
Plan We need to write the ions present in the

reactants and exchange the anions between the
two cations. Once we have written the chemical
formulas for these products, we can use
Table 4.1 to determine which is insoluble in
water. Knowing the products also allows us to
write the equation for the reaction.
Solve
(a) The reactants contain Ba2+, Cl–, K+, and
SO42– ions. Exchanging the anions gives
us BaSO4 and KCl. According to Table 4.1, most compounds of SO 42– are soluble but those of Ba2+ are not. Thus,
BaSO4 is insoluble and will precipitate from solution. KCl is soluble.
(b) From part (a) we know the chemical formulas of the products, BaSO 4 and KCl. The balanced equation is
BaCl2(aq) + K2SO4(aq) BaSO4(s) + 2 KCl(aq)

Sample Exercise 4.3 Predicting a Metathesis Reaction
Continued
Practice Exercise
(a) What compound precipitates when aqueous solutions of Fe 2(SO4)3 and LiOH are mixed? (b) Write a balanced
equation for the reaction.

Ways to Write Equations for
Metathesis Reactions
1) Molecular equation
2) Complete ionic equation
3) Net ionic equation

Molecular Equation
• The molecular equation lists the reactants and
products without indicating the ionic nature of the
compounds.
• The only indication of the overall reaction is the states
of matter given.

Complete Ionic Equation
• In the complete ionic equation all strong electrolytes
(strong acids, strong bases, and soluble ionic salts)
are dissociated into their ions.
• This more accurately reflects the species that are
found in the reaction mixture.

Net Ionic Equation
• To form the net ionic equation, cross out anything that
does not change from the left side of the equation to
the right.
• The ions crossed out are called spectator ions, K+
and NO3−, in this example.
• The remaining ions are the reactants that form the
product—an insoluble salt in a precipitation reaction,
as in this example.

How to Write a Net Ionic Equation
1) Write a balanced molecular equation for the
reaction.
2) Rewrite the equation to show the ions that form in
solution when each soluble strong electrolyte
dissociates into its ions. Only strong electrolytes
dissolved in aqueous solution are written in ionic
form.
3) Identify and cancel spectator ions.

Sample Exercise 4.4 Writing a Net Ionic Equation
Write the net ionic equation for the precipitation reaction that occurs when aqueous solutions of
calcium chloride and sodium carbonate are mixed.
Solution
Analyze Our task is to write a net ionic equation for a precipitation reaction, given the names of the reactants present
in solution.
Plan We write the chemical formulas of the reactants and products and then determine which product is insoluble. We
then write and balance the molecular equation. Next, we write each soluble strong electrolyte as separated ions to
obtain the complete ionic equation. Finally, we eliminate the spectator ions to obtain the net ionic equation.
Solve Calcium chloride is composed of calcium ions, Ca 2+, and chloride ions, Cl–; hence, an aqueous solution of the
substance is CaCl2(aq). Sodium carbonate is composed of Na + ions and CO32– ions; hence, an aqueous solution of the
compound is Na2CO3(aq). In the molecular equations for precipitation reactions, the anions and cations appear to
exchange partners. Thus, we put Ca2+ and CO32–
together to give CaCO3 and Na+ and Cl– together
to give NaCl. According to the solubility
guidelines in Table 4.1, CaCO3 is insoluble and
NaCl is soluble. The balanced molecular equation is
CaCl2(aq) + Na2CO3(aq)
CaCO3(s) + 2 NaCl(aq)

Continued
In a complete ionic equation, only dissolved strong electrolytes (such as soluble ionic compounds) are written as
separate ions. As the (aq) designations remind us, CaCl 2, Na2CO3, and NaCl are all dissolved in the solution.
Furthermore, they are all strong electrolytes. CaCO 3 is an ionic compound, but it is not soluble. We do not write the
formula of any insoluble compound as its component ions. Thus, the complete ionic equation is
Ca2+(aq) + 2 Cl–(aq) + 2 Na+(aq) + CO32–(aq) CaCO3(s) + 2 Na+(aq) + 2 Cl–(aq)
The spectator ions are Na+ and Cl–. Canceling them gives the following net ionic equation:
Ca2+(aq) + CO32–(aq) CaCO3(s)
Check We can check our result by confirming that both the elements and the electric charge are balanced. Each side
has one Ca, one C, and three O, and the net charge on each side equals 0.
Comment If none of the ions in an ionic equation is removed from solution or changed in some way, all ions are
spectator ions and a reaction does not occur.

Continued
Practice Exercise
Write the net ionic equation for the precipitation reaction that occurs when aqueous solutions of silver nitrate and
potassium phosphate are mixed.

Acids and Bases
• Vinegar and lemon juice are common household acids.
Ammonia and baking soda (sodium bicarbonate) are
common household bases.

Acids
• Acids as substances that ionize in aqueous solution
to form H+
• Because H+ consists of ONLY a proton, acids are
often called proton donors.
Figure 4.4 Molecular models of four common acids.

Bases
• Bases are substances that react with, or accept,
H+ ions; they increase the concentration of OH–
when dissolved in water.
• Substances do NOT have to contain OH– to be
a base.
Figure 4.5 Proton transfer.

Strong or Weak?
• Strong acids completely dissociate in water; weak
acids only partially dissociate.
• Strong bases dissociate to metal cations and
hydroxide anions in water; weak bases only partially
react to produce hydroxide anions.

Strong or Weak Electrolyte?
1) Is the substance ionic or molecular? If it is ionic, it is
a strong electrolyte. (Solubility?)
2) Molecular: is it an acid or a base?
3) If it starts with H or ends in COOH, it is an acid. If it
is NOT on the list of strong acids, it is a weak acid.
(Strong acid = strong electrolyte; weak acid = weak
electrolyte.)
4) Strong bases (Table 4.2) are strong electrolytes; NH3
is a weak base (weak electrolyte).

Strong or Weak Electrolyte?

Sample Exercise 4.5 Comparing Acid Strengths
The following diagrams represent aqueous solutions of acids HX, HY, and HZ, with water molecules omitted for
clarity. Rank the acids from strongest to weakest.
Solution
Analyze We are asked to rank three acids from strongest to weakest, based on schematic drawings of their solutions.
Plan We can determine the relative numbers of uncharged molecular species in the diagrams. The strongest acid is the
one with the most H+ ions and fewest undissociated molecules in solution. The weakest acid is the one with the largest
number of undissociated molecules.
Solve The order is HY > HZ > HX. HY is a strong acid because it is totally ionized (no HY molecules in solution),
whereas both HX and HZ are weak acids, whose solutions consist of a mixture of molecules and ions. Because HZ
contains more H+ ions and fewer molecules than HX, it is a stronger acid.

Sample Exercise 4.5 Comparing Acid Strengths
Continued
Practice Exercise
A set of aqueous solutions are prepared containing different acids at the same concentration: acetic acid, chloric acid,
and hydrobromic acid. Which solution(s) are the most electrically conductive? (a) chloric acid (b) hydrobromic acid
(c) acetic acid (d) both chloric acid and hydrobromic acid (e) all three solutions have the same electrical conductivity

Sample Exercise 4.6 Identifying Strong, Weak, and Nonelectrolytes
Classify these dissolved substances as a strong electrolyte, weak electrolyte, or nonelectrolyte: CaCl 2, HNO3,
C2H5OH (ethanol), HCOOH (formic acid), KOH.
Solution
Analyze We are given several chemical formulas and asked to classify each substance as a strong electrolyte, weak
electrolyte, or nonelectrolyte.
Plan The approach we take is outlined in Table 4.3. We can predict whether a substance is ionic or molecular based on
its composition. As we saw in Section 2.7, most ionic compounds we encounter in this text are composed of a metal
and a nonmetal, whereas most molecular compounds are composed only of nonmetals.
Solve Two compounds fit the criteria for ionic compounds: CaCl 2 and KOH. Because Table 4.3 tells us that all ionic
compounds are strong electrolytes, that is how we classify these two substances. The three remaining compounds are
molecular. Two of these molecular substances, HNO 3 and HCOOH, are acids. Nitric acid, HNO3, is a common strong
acid, as shown in Table 4.2, and therefore is a strong electrolyte. Because most acids are weak acids, our best guess
would be that HCOOH is a weak acid (weak electrolyte), which is in fact the case. The remaining molecular
compound, C2H5OH, is neither an acid nor a base, so it is a nonelectrolyte.

Sample Exercise 4.6 Identifying Strong, Weak, and Nonelectrolytes
Continued
Comment Although ethanol, C2H5OH, has an OH group, it is not a metal hydroxide and therefore not a base. Rather,
ethanol is a member of a class of organic compounds that have C—OH bonds, which are known as alcohols.
(Section 2.9) Organic compounds containing the COOH group are called carboxylic acids (Chapter 16).
Molecules that have this group are weak acids.
Practice Exercise
Which of these substances, when dissolved in water, is a strong electrolyte? (a) ammonia (b) hydrofluoric acid
(c) folic acid (d) sodium nitrate (e) sucrose

Neutralization Reactions
• The properties of acidic and
basic solutions are different.
• Acids have a sour taste,
whereas bases have a bitter
taste.
• Acids change the colors of
certain dyes in a way that
differs from the way bases
affect the same dyes.
• This is the principle behind Figure 4.6 Litmus paper.
the indicator known as litmus
paper.

• Reactions between an acid and a base are called
neutralization reactions.
• When the base is a metal hydroxide, water and a salt
(an ionic compound) are produced.
• These equations can be written as molecular,
complete ionic, or net ionic equations.

Figure 4.7 Neutralization reaction between Mg(OH)2(s) and hydrochloric acid.

Sample Exercise 4.7 Writing Chemical Equations for a Neutralization
Reaction
For the reaction between aqueous solutions of acetic acid (CH 3COOH) and barium hydroxide, Ba(OH)2, write
(a) the balanced molecular equation, (b) the complete ionic equation, (c) the net ionic equation.
Solution
Analyze We are given the chemical formulas for an acid and a base and asked to write a balanced molecular equation,
a complete ionic equation, and a net ionic equation for their neutralization reaction.
Plan As Equation 4.11 and the italicized statement that follows it indicate, neutralization reactions form two products,
H2O and a salt. We examine the cation of the base and the anion of the acid to determine the composition of the salt.
Solve
(a) The salt contains the cation of the base (Ba 2+) and the anion of the acid (CH3COO–). Thus, the salt formula is
Ba(CH3COO)2. According to Table 4.1, this compound is soluble in water. The unbalanced molecular equation for
the neutralization reaction is:
CH3COOH(aq) + Ba(OH)2(aq)
H2O(l) + Ba(CH3COO)2(aq)

Reaction
Continued
To balance this equation, we must provide two molecules of CH 3COOH to furnish the two CH3COO– ions and to
supply the two H+ ions needed to combine with the two OH– ions of the base. The balanced molecular equation is:
2 CH3COOH(aq) + Ba(OH)2(aq) 2 H2O(l) + Ba(CH3COO)2(aq)
(b) To write the complete ionic equation, we identify the strong electrolytes and break them into ions. In this case
Ba(OH)2 and Ba(CH3COO)2 are both water-soluble ionic compounds and hence strong electrolytes. Thus, the
complete ionic equation is:
2 CH3COOH(aq) + Ba2+(aq) + 2OH–(aq) 2 H2O(l) + Ba2+(aq) + 2 CH3COO–(aq)
(c) Eliminating the spectator ion, Ba 2+, and simplifying coefficients give the net ionic equation:
CH3COOH(aq) + OH–(aq) H2O(l) + CH3COO–(aq)
Check We can determine whether the molecular equation is balanced by counting the number of atoms of each kind on
both sides of the arrow (10 H, 6 O, 4 C, and 1 Ba on each side). However, it is often easier to check equations by
counting groups: There are 2 CH3COO groups, as well as 1 Ba, and 4 additional H atoms and 2 additional O atoms on
each side of the equation. The net ionic equation checks out because the numbers of each kind of element and the net
charge are the same on both sides of the equation.

Reaction
Continued
Practice Exercise
Which is the correct net ionic equation for the reaction of aqueous ammonia with nitric acid?
(a) NH4+(aq) + H+(aq) NH52+(aq)
(b) NH3(aq) + NO3–(aq) NH2–(aq) + HNO3(aq)
(c) NH2–(aq) + H+(aq) NH3(aq)
(d) NH3(aq) + H+(aq) NH4+(aq)
(e) NH4+(aq) + NO3–(aq) NH4NO3(aq)

Neutralization Reactions with
Gas Formation
• Sulfide ion and the carbonate ion react with acids to form
gases that have low solubilities in water.
• Hydrogen sulfide (H2S), the substance that gives rotten
eggs their foul odor, forms when an acid such as HCl(aq)
reacts with a metal sulfide such as Na2S:

Neutralization Reactions with
Gas Formation
• When a carbonate or bicarbonate reacts with an acid,
the products are a salt, carbon dioxide, and water.

Application of Neutralization Reactions:
Antacids
• We can address the problem of excess stomach acid in
two ways: (1) removing the excess acid or (2) decreasing
the production of acid.
• Substances that remove excess acid are called antacids,
whereas those that decrease acid production are called
acid inhibitors.
Figure 4.8 Antacids.

Oxidation-Reduction Reactions
• Loss of electrons is oxidation.
• Gain of electrons is reduction.
• One cannot occur without the other.
• The reactions are often called redox reactions.
Figure 4.10 Oxidation of calcium metal by molecular oxygen.

Oxidation-Reduction Reactions
• Familiar redox reactions
(a) A green coating forms when copper is oxidized.
(b) Rust forms when iron corrodes.
(c) A black tarnish forms as silver corrodes.
Figure 4.9 Familiar corrosion products.

Oxidation Numbers
• To determine if an oxidation-reduction reaction has
occurred, we assign an oxidation number to each
element in a neutral compound or charged entity.
• This is a “bookkeeping” method—it does NOT imply
that the atoms have these charges!

Rules to Assign Oxidation Numbers
1) Atoms in their elemental form have an oxidation
number of 0.
2) The oxidation number of a monatomic ion is the
same as its charge.

3) Nonmetals usually have negative oxidation numbers,
although they sometimes can be positive:
– Oxygen: usually −2, except in the peroxide ion, where it
is −1.
– Hydrogen: usually +1 when bonded to a nonmetal and
−1 when bonded to a metal.
– Fluorine: –1. Other halogens: usually –1, unless
combined with oxygen (oxyanions), where they will be
positive.

4) The sum of the oxidation numbers in a neutral
compound is zero; the sum of the oxidation numbers
in a polyatomic ion is the charge on the ion.
(Remember to count EVERY atom, no matter how large
the subscript, when assigning oxidation numbers!)

Sample Exercise 4.8 Determining Oxidation Numbers
Determine the oxidation number of sulfur in (a) H2S, (b) S8, (c) SCl2, (d) Na2SO3, (e) SO42–.
Solution
Analyze We are asked to determine the oxidation number of sulfur in two molecular species, in the elemental form,
and in two substances containing ions.
Plan In each species, the sum of oxidation numbers of all the atoms must equal the charge on the species. We will use
the rules outlined previously to assign oxidation numbers.
Solve
(a) When bonded to a nonmetal, hydrogen has an oxidation number of +1. Because the H 2S molecule is neutral, the
sum of the oxidation numbers must equal zero. Letting x equal the oxidation number of S, we have 2(+1) + x = 0.
Thus, S has an oxidation number of –2.
(b) Because S8 is an elemental form of sulfur, the oxidation number of S is 0.
(c) Because SCl2 is a binary compound, we expect chlorine to have an oxidation number of –1. The sum of the
oxidation numbers must equal zero. Letting x equal the oxidation number of S, we have x + 2(–1) = 0.
Consequently, the oxidation number of S must be +2.
(d) Sodium, an alkali metal, always has an oxidation number of +1 in its compounds. Oxygen commonly has an
oxidation state of –2. Letting x equal the oxidation number of S, we have 2(+1) + x + 3(–2) = 0. Therefore, the
oxidation number of S in this compound (Na 2SO3) is +4.
(e) The oxidation state of O is –2. The sum of the oxidation numbers equals –2, the net charge of the SO 42– ion. Thus,
we have x + 4(–2) = –2. From this relation we conclude that the oxidation number of S in this ion is +6.

Sample Exercise 4.8 Determining Oxidation Numbers
Continued
Comment These examples illustrate that the oxidation number of a given element depends on the compound in which
it occurs. The oxidation numbers of sulfur, as seen in these examples, range from –2 to +6.
Practice Exercise
In which compound is the oxidation state of oxygen –1?
(a) O2 (b) H2O (c) H2SO4 (d) H2O2 (e) KCH3COO

Displacement Reactions
• In displacement reactions, ions oxidize an element.
(H+ oxidizes Mg below.)
• The ion is displaced (replaced) in solution.
(Mg replaces H+ below.)

Displacement Reactions
Figure 4.11 Reaction of magnesium metal with hydrochloric acid.

Sample Exercise 4.9 Writing Equations for Oxidation-Reduction
Reactions
Write the balanced molecular and net ionic equations for the reaction of aluminum with hydrobromic acid.
Solution
Analyze We must write two equations—molecular and net ionic—for the redox reaction between a metal and an acid.
Plan Metals react with acids to form salts and H 2 gas. To write the balanced equations, we must write the chemical
formulas for the two reactants and then determine the formula of the salt, which is composed of the cation formed by
the metal and the anion of the acid.
Solve The reactants are Al and HBr. The cation formed by Al is Al 3+, and the anion from hydrobromic acid is Br –.
Thus, the salt formed in the reaction is AlBr 3. Writing the reactants and products and then balancing the equation gives
the molecular equation:
2 Al(s) + 6 HBr(aq) 2 AlBr3(aq) + 3 H2(g)
Both HBr and AlBr3 are soluble strong electrolytes. Thus, the complete ionic equation is
2 Al(s) + 6 H+(aq) + 6 Br–(aq) 2 Al3+(aq) + 6 Br–(aq) + 3 H2(g)
Because Br– is a spectator ion, the net ionic equation is
2 Al(s) + 6 H+(aq) 2 Al3+(aq) + 3 H2(g)

Sample Exercise 4.9 Writing Equations for Oxidation-Reduction
Reactions
Continued
Comment The substance oxidized is the aluminum metal because its oxidation state changes from 0 in the metal to +3
in the cation, thereby increasing in oxidation number. The H + is reduced because its oxidation state changes from +1 in
the acid to 0 in H2.
Practice Exercise
Which of the following statements is true about the reaction between zinc and copper sulfate? (a) Zinc is oxidized, and
copper ion is reduced. (b) Zinc is reduced, and copper ion is oxidized. (c) All reactants and products are soluble strong
electrolytes. (d) The oxidation state of copper in copper sulfate is 0. (e) More than one of the previous choices are true.

Activity Series and Hydrogen
• The elements above

hydrogen will react with
acids to produce
hydrogen gas.
• Elements below will
NOT react!
• A reactive metal is
oxidized to a cation.

Metal/Acid Displacement Reactions
• Elements higher on the activity series are more
reactive.
• They will exist as ions.
• The element below will exist as the element.
Figure 4.12 Reaction

of copper metal with
silver ion.
Sample Exercise 4.10 Determining If an Oxidation-Reduction
Reaction Will Occur
Will an aqueous solution of iron(II) chloride oxidize magnesium metal? If so, write the balanced molecular and net
ionic equations for the reaction.
Solution
Analyze We are given two substances—an aqueous salt, FeCl 2, and a metal, Mg—and asked if they react with
each other.
Plan A reaction occurs if the reactant that is a metal in its

elemental form (Mg) is located above the reactant that is a
metal in its oxidized form (Fe2+) in Table 4.5. If the reaction
occurs, the Fe2+ ion in FeCl2 is reduced to Fe, and the Mg is
oxidized to Mg2+.

Reaction Will Occur
Continued
Solve Because Mg is above Fe in the table, the reaction occurs. To write the formula for the salt produced in the
reaction, we must remember the charges on common ions. Magnesium is always present in compounds as Mg 2+; the
chloride ion is Cl–. The magnesium salt formed in the reaction is MgCl 2, meaning the balanced molecular equation is
Mg(s) + FeCl2(aq) MgCl2(aq) + Fe(s)
Both FeCl2 and MgCl2 are soluble strong electrolytes and can be written in ionic form, which shows us that Cl – is a
spectator ion in the reaction. The net ionic equation is
Mg(s) + Fe2+ (aq) Mg2+ (aq) + Fe(s)
The net ionic equation shows that Mg is oxidized and Fe 2+ is reduced in this reaction.
Check Note that the net ionic equation is balanced with respect to both charge and mass.

Reaction Will Occur
Continued
Practice Exercise
Which of these metals is the easiest to oxidize? (a) gold (b) lithium (c) iron (d) sodium (e) aluminum

Molarity
• The quantity of solute in a solution can matter to a
chemist.
• We call the amount dissolved its concentration.
• Molarity is one way to measure the concentration of
a solution:
• Molarity can be used as a conversion factor between

moles and liters.

Mixing a Solution
• To create a solution of a known molarity, weigh out a known
mass (and, therefore, number of moles) of the solute.
• Then add solute to a volumetric flask, and add solvent to the
line on the neck of the flask.
(0.250 mol CuSO4) / (0.250 L

solution) = 1.00 M
Figure 4.13 Preparing 0.250 L

of a 1.00 M solution of CuSO4.
Sample Exercise 4.11 Calculating Molarity
Calculate the molarity of a solution made by dissolving 23.4 g of sodium sulfate (Na 2SO4) in enough water to form
125 mL of solution.
Solution
Analyze We are given the number of grams of solute (23.4 g), its chemical formula (Na 2SO4), and the volume of the
solution (125 mL) and asked to calculate the molarity of the solution.
Plan We can calculate molarity using Equation 4.31. To do so, we must convert the number of grams of solute to
moles and the volume of the solution from milliliters to liters.
Solve
The number of moles of Na2SO4 is obtained by using its molar mass:
Converting the volume of the solution to liters:
Thus, the molarity is:

Sample Exercise 4.11 Calculating Molarity
Continued
Check Because the numerator is only slightly larger than the denominator, it is reasonable for the answer to be a little
over 1 M. The units (mol/L) are appropriate for molarity, and three significant figures are appropriate for the answer
because each of the initial pieces of data had three significant figures.
Practice Exercise
What is the molarity of a solution that is made by dissolving 3.68 g of sucrose (C 12H22O11) in sufficient water to form
275.0 mL of solution? (a) 13.4 M (b) 7.43 × 10–2 M (c) 3.91 × 10–2 M (d) 7.43 × 10–5 M (e) 3.91 × 10–5 M

Sample Exercise 4.12 Calculating Molar Concentrations of Ions
What is the molar concentration of each ion present in a 0.025 M aqueous solution of calcium nitrate?
Solution
Analyze We are given the concentration of the ionic compound used to make the solution and asked to determine the
concentrations of the ions in the solution.
Plan We can use the subscripts in the chemical formula of the compound to determine the relative ion concentrations.
Solve Calcium nitrate is composed of calcium ions (Ca 2+) and nitrate ions (NO3–), so its chemical formula is Ca(NO3)2.
Because there are two NO3– ions for each Ca2+ ion, each mole of Ca(NO3)2 that dissolves dissociates into 1 mol of Ca 2+
and 2 mol of NO3–. Thus, a solution that is 0.025 M in Ca(NO3)2 is 0.025 M in Ca2+ and 2 × 0.025 M = 0.050 M in
NO3–:
Check The concentration of NO3– ions is twice that of Ca2+ ions, as the subscript 2 after the NO3– in the chemical
formula Ca(NO3)2 suggests.

Sample Exercise 4.12 Calculating Molar Concentrations of Ions
Continued
Practice Exercise
What is the ratio of the concentration of potassium ions to the concentration of carbonate ions in a 0.015 M solution of
potassium carbonate? (a) 1:0.015 (b) 0.015:1 (c) 1:1 (d) 1:2 (e) 2:1

Sample Exercise 4.13 Using Molarity to Calculate Grams of
Solute
How many grams of Na2SO4 are required to make 0.350 L of 0.500 M Na2SO4?
Solution
Analyze We are given the volume of the solution (0.350 L), its concentration (0.500 M), and the identity of the solute
Na2SO4 and asked to calculate the number of grams of the solute in the solution.
Plan We can use the definition of molarity (Equation 4.31) to determine the number of moles of solute, and then
convert moles to grams using the molar mass of the solute.
Solve Calculating the moles of Na2SO4 using the molarity and volume of solution gives

Sample Exercise 4.13 Using Molarity to Calculate Grams
of Solute
Continued
Because each mole of Na2SO4 has a mass of 142.1 g, the required number of grams of Na 2SO4 is
Check The magnitude of the answer, the units, and the number of significant figures are all appropriate.
Practice Exercise
(a) How many grams of Na2SO4 are there in 15 mL of 0.50 M Na2SO4? (b) How many milliliters of 0.50 M Na2SO4
solution are needed to provide 0.038 mol of this salt?

Dilution
A solution can be diluted by adding ONLY solvent. The
concentration is LOWER, but the MOLES don’t change.
Figure 4.14 Preparing 250.0 mL of 0.100 M CuSO4 by dilution of 1.00 M CuSO4.

Dilution
• The molarity of the new solution can be determined
from the equation
Moles solute before dilution = moles solute after dilution
Remember: M × V (in L) = moles

Sample Exercise 4.14 Preparing a Solution by Dilution
How many milliliters of 3.0 M H2SO4 are needed to make 450 mL of 0.10 M H2SO4?
Solution
Analyze We need to dilute a concentrated solution. We are given the molarity of a more concentrated solution (3.0 M)
and the volume and molarity of a more dilute one containing the same solute (450 mL of 0.10 M solution). We must
calculate the volume of the concentrated solution needed to prepare the dilute solution.
Plan We can calculate the number of moles of solute, H 2SO4, in the dilute solution and then calculate the volume of
the concentrated solution needed to supply this amount of solute. Alternatively, we can directly apply Equation 4.33.
Let’s compare the two methods.
Solve Calculate the moles of H2SO4 in the dilute solution:
Calculate the volume of the concentrated solution that contains 0.045 mol H 2SO4:
Converting liters to milliliters gives 15 mL.

Sample Exercise 4.14 Preparing a Solution by Dilution
Continued
If we apply Equation 4.33, we get the same result:
Either way, we see that if we start with 15 mL of 3.0 M H2SO4 and dilute it to a total volume of 450 mL, the desired
0.10 M solution will be obtained.
Check The calculated volume seems reasonable because a small volume of concentrated solution is used to prepare a
large volume of dilute solution.
Comment The first approach can also be used to find the final concentration when two solutions of different
concentrations are mixed, whereas the second approach, using Equation 4.33, can be used only for diluting a
concentrated solution with pure solvent.
Practice Exercise
What volume of a 1.00 M stock solution of glucose must be used to make 500.0 mL of a 1.75 × 10 –2 M glucose
solution in water?
(a) 1.75 mL (b) 8.75 mL (c) 48.6 mL (d) 57.1 mL (e) 28,570 mL

Stoichiometry Applied to Solutions
Figure 4.15 Procedure for solving stoichiometry problems involving reactions

between a pure substance A and a solution containing a known concentration of
substance B.
Sample Exercise 4.15 Using Mass Relations in a Neutralization
Reaction
How many grams of Ca(OH)2 are needed to neutralize 25.0 mL of 0.100 M HNO3?
Solution
Analyze The reactants are an acid, HNO3, and a base, Ca(OH)2. The volume and molarity of HNO3 are given, and we
are asked how many grams of Ca(OH)2 are needed to neutralize this quantity of HNO 3.
Plan Following the steps outlined by the green arrows in Figure 4.17, we use the molarity and volume of the HNO 3
solution (substance B in Figure 4.17) to calculate the number of moles of HNO 3. We then use the balanced equation to
relate moles of HNO3 to moles of Ca(OH)2 (substance A). Finally, we use the molar mass to convert moles to grams of
Ca(OH)2:
Solve
The product of the molar concentration of a solution and its volume in liters gives
the number of moles of solute:

Sample Exercise 4.15 Using Mass Relations in a Neutralization
Reaction
Continued
Because this is a neutralization reaction, HNO 3 and Ca(OH)2 react to form H2O and the salt containing Ca2+ and NO3–:
2 HNO3(aq) + Ca(OH)2(s) 2 H2O(l) + Ca(NO3)2(aq)
Thus, 2 mol HNO3 1 mol Ca(OH)2. Therefore,
Check The answer is reasonable because a small volume of dilute acid requires only a small amount of base to
neutralize it.
Practice Exercise
How many milligrams of sodium sulfide are needed to completely react with 25.00 mL of a 0.0100 M aqueous solution
of cadmium nitrate, to form a precipitate of CdS(s)? (a) 13.8 mg (b) 19.5 mg (c) 23.5 mg (d) 32.1 mg (e) 39.0 mg

Titration
• A titration is an analytical technique in which one can
calculate the concentration of a solute in a solution.
Figure 4.16 Procedure for titrating an acid against a standard solution of NaOH.
Titration
• A solution of known concentration, called a standard
solution, is used to determine the unknown concentration
of another solution.
• The reaction is complete at the equivalence point, which
is based on the seen end point (color change).
Figure 4.17 Procedure for determining the concentration of a solution from

titration with a standard solution.
Sample Exercise 4.16 Determining Solution Concentration by an
Acid–Base Titration
One commercial method used to peel potatoes is to soak them in a NaOH solution for a short time and then remove the
potatoes and spray off the peel. The NaOH concentration is normally 3 to 6 M, and the solution must be analyzed
periodically. In one such analysis, 45.7 mL of 0.500 M H2SO4 is required to neutralize 20.0 mL of NaOH solution.
What is the concentration of the NaOH solution?
Solution
Analyze We are given the volume (45.7 mL) and molarity (0.500 M) of an H2SO4 solution (the standard solution) that
reacts completely with 20.0 mL of NaOH solution. We are asked to calculate the molarity of the NaOH solution.
Plan Following the steps given in Figure 4.19, we use the H 2SO4
volume and molarity to calculate the number of moles of H 2SO4.
Then we can use this quantity and the balanced equation for the
reaction to calculate moles of NaOH. Finally, we can use moles
of NaOH and the NaOH volume to calculate NaOH molarity.
Solve
The number of moles of H2SO4 is the product of the volume and
molarity of this solution:

Continued
Acids react with metal hydroxides to form water and a salt. Thus, the balanced equation for the neutralization
reaction is:
H2SO4(aq) + 2 NaOH(aq) 2 H2O(l) + Na2SO4(aq)
According to the balanced equation, 1 mol H2SO4 2 mol NaOH. Therefore,
Knowing the number of moles of NaOH in 20.0 mL of solution allows us to calculate the molarity of this solution:

Continued
Practice Exercise
What is the molarity of an HCl solution if 27.3 mL of it neutralizes 134.5 mL of 0.0165 M Ba(OH)2?
(a) 0.0444 M (b) 0.0813 M (c) 0.163 M (d) 0.325 M (e) 3.35 M

Sample Exercise 4.17 Determining the Quantity of Solute by Titration
The quantity of Cl– in a municipal water supply is determined by titrating the sample with Ag +. The precipitation
reaction taking place during the titration is
Ag+(aq) + Cl–(aq) AgCl(s)
(a) How many grams of chloride ion are in a sample of the water if 20.2 mL of 0.100 M Ag+ is needed to react with
all the chloride in the sample? (b) If the sample has a mass of 10.0 g, what percentage of Cl – does it contain?
Solution
Analyze We are given the volume (20.2 mL) and molarity (0.100 M) of a solution of Ag + and the chemical equation
for reaction of this ion with Cl –. We are asked to calculate the number of grams of Clin the sample and the mass
percentage of Cl– in the sample.
Plan (a) We can use the procedure outlined by the green arrows in
Figure 4.17. We begin by using the volume and molarity of Ag + to
calculate the number of moles of Ag + used in the titration. We then
use the balanced equation to determine the moles of Cl – in the
sample and from that the grams of Cl –. (b) To calculate the
percentage of Cl– in the sample, we compare the number
of grams of Cl– in the sample with the original mass of
the sample, 10.0 g.

Continued
Solve
(a) Calculate the number of moles of Ag + used in the titration.
From the balanced equation we see that 1 mol Ag + 1 mol Cl–. Using this information and the molar
mass of Cl, we have:
(b) Calculate the percentage of Cl – used in the sample.

Continued
Practice Exercise
A mysterious white powder is found at a crime scene. A simple chemical analysis concludes that the powder is a
mixture of sugar and morphine (C17H19NO3), a weak base similar to ammonia. The crime lab takes 10.00 mg of the
mysterious white powder, dissolves it in 100.00 mL water, and titrates it to the equivalence point with 2.84 mL of a
standard 0.0100 M HCl solution. What is the percentage of morphine in the white powder?
(a) 8.10%
(b) 17.3%
(c) 32.6%
(d) 49.7%
(e) 81.0%

Sample Integrative Exercise Putting Concepts Together
Note: Integrative exercises require skills from earlier chapters as well as ones from the present chapter. A
sample of 70.5 mg of potassium phosphate is added to 15.0 mL of 0.050 M silver nitrate, resulting in the
formation of a precipitate. (a) Write the molecular equation for the reaction. (b) What is the limiting reactant
in the reaction? (c) Calculate the theoretical yield, in grams, of the precipitate that forms.
Solution
(a) Potassium phosphate and silver nitrate are both ionic compounds. Potassium phosphate contains K + and PO43–
ions, so its chemical formula is K3PO4. Silver nitrate contains Ag+ and NO3– ions, so its chemical formula is
AgNO3. Because both reactants are strong electrolytes, the solution contains K +, PO43–, Ag+, and NO3– ions before
the reaction occurs. According to the solubility guidelines in Table 4.1, Ag+ and PO 43– form an insoluble
compound, so Ag3PO4 will precipitate from the solution. In contrast, K + and NO3– will remain in solution because
KNO3 is water soluble. Thus, the balanced molecular equation for the reaction is:
K3PO4(aq) + 3 AgNO3(aq) Ag3PO4(s) + 3 KNO3(aq)

Continued
(b) To determine the limiting reactant, we must examine the number of moles of each reactant. (Section 3.7) The
number of moles of K3PO4 is calculated from the mass of the sample using the molar mass as a conversion factor.
(Section 3.4) The molar mass of K3PO4 is 3(39.1) + 31.0 + 4(16.0) = 212.3 g/mol. Converting milligrams to
grams and then to moles, we have:
We determine the number of moles of AgNO3 from the volume and molarity of the solution. (Section 4.5)
Converting milliliters to liters and then to moles, we have:
Comparing the amounts of the two reactants, we find that there are (7.5 × 10 –4)/(3.32 × 10–4) = 2.3 times as many
moles of AgNO3 as there are moles of K3PO4. According to the balanced equation, however, 1 mol K 3PO4 requires
3 mol AgNO3. Thus, there is insufficient AgNO3 to consume the K3PO4, and AgNO3 is the limiting reactant.

Continued
(c) The precipitate is Ag3PO4, whose molar mass is 3(107.9) + 31.0 + 4(16.0) = 418.7 g/mol. To calculate the number
of grams of Ag3PO4 that could be produced in this reaction (the theoretical yield), we use the number of moles of
the limiting reactant, converting mol AgNO 3 mol Ag3PO4 g Ag3PO4. We use the coefficients in the balanced
equation to convert moles of AgNO3 to moles Ag3PO4, and we use the molar mass of Ag3PO4 to convert the
number of moles of this substance to grams.
The answer has only two significant figures because the quantity of AgNO 3 is given to only two significant
figures.

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Chapter 4

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Figure 4.2 Dissolution in water.

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NaCl(s) → Na+(aq) + Cl － (aq)

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Plan We examine each ionic substance given to determine the

Solve The diagram shows twice as many cations as anions,

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Figure 4.3 A precipitation reaction.

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(b) Table 4.1 indicates that although most

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Plan We need to write the ions present in the

BaCl2(aq) + K2SO4(aq) BaSO4(s) + 2 KCl(aq)

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Ca2+(aq) + 2 Cl–(aq) + 2 Na+(aq) + CO32–(aq) CaCO3(s) + 2 Na+(aq) + 2 Cl–(aq)

Ca2+(aq) + CO32–(aq) CaCO3(s)

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Figure 4.4 Molecular models of four common acids.

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Figure 4.5 Proton transfer.

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Figure 4.7 Neutralization reaction between Mg(OH)2(s) and hydrochloric acid.

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2 CH3COOH(aq) + Ba(OH)2(aq) 2 H2O(l) + Ba(CH3COO)2(aq)

2 CH3COOH(aq) + Ba2+(aq) + 2OH–(aq) 2 H2O(l) + Ba2+(aq) + 2 CH3COO–(aq)