Chapter 4

Chapter 4
Reactions In Aqueous Solutions
Aqueous
Reactions
4.1: General properties of Aqueous
Solutions
• Solutions are defined as homogeneous mixtures of two or
more pure substances.
• A solution is formed from a solute(s) dissolved in a solvent.
• The solvent is present in greatest abundance.
• All other substances are solutes.
Aqueous
Reactions
In aqueous solutions (aq)
•solvent is water
•solute can be ionic compounds, aqueous acids,
bases, or molecular compounds
 Water is one of the most common solvent
 It’s a polar molecule
O - a hydrogen bond
H +
Aqueous
H + Reactions
“Like dissolves like”
A solvent such as water is needed to dissolve

polar solutes such as sugar and ionic solutes
such as NaCl.
A solvent such as hexane (C6H14) is needed to

dissolve nonpolar solutes such as oil or grease.
Aqueous
Reactions
Learning Check
Which of the following solutes will

dissolve in water? Why?
1) Na2SO4
2) gasoline
3) I2
4) HCl
Aqueous
Reactions
Which of the following solutes will
dissolve in water? Why?
1) Na2SO4 Yes, polar (ionic)

2) gasoline No, nonpolar
3) I2 No, nonpolar
4) HCl Yes, polar
Aqueous
Reactions
Dissociation
• When an ionic
substance dissolves in
water, the solvent pulls
the individual ions from
the crystal and solvates
them.
• This process is called
dissociation.
Aqueous
Reactions
Dissociation
• An electrolyte is a
substances that
dissociates into
ions when
dissolved in water.
Aqueous
Reactions
© 2012 Pearson Education, Inc.
Solutions
• A non- electrolyte
may dissolve in
water, but it does not
dissociate into ions
when it does so.
Aqueous
Reactions
Electrolytes and Non- electrolytes
• Soluble ionic compounds tend to be

electrolytes.
• Molecular compounds tend to be
nonelectrolytes, except for acids and bases.
Aqueous
Reactions
Electrolytes
• A strong electrolyte dissociates completely

when dissolved in water.
• A weak electrolyte only dissociates partially
when dissolved in water.
Aqueous
Reactions
Strong Electrolytes Are…
• Strong acids
• Strong bases
• Soluble ionic salts
Aqueous
Reactions
4.2: Solubility Rules
1. Group IA and ammonium compounds are
soluble.
2. Acetates and nitrates are soluble.
3. Most chlorides, bromides, and iodides are
soluble.
Exceptions:
AgCl, Hg2Cl2, PbCl2;
AgBr, HgBr2, Hg2Br2, PbBr2;
AgI, HgI2, Hg2I2, PbI2
4. Most sulfates are soluble.
Exceptions:
CaSO4, SrSO4, BaSO4,
Ag2SO4, Hg2SO4, PbSO4
Copyright © Cengage Learning. All rights reserved. 4 | 13
5. Most carbonates are insoluble.
Exceptions:
Group IA carbonates and (NH4)2CO3
6. Most phosphates are insoluble.
Exceptions:
Group IA phosphates and (NH4)3PO4
7. Most sulfides are insoluble.
Exceptions:
Group IA sulfides and (NH4)2S
8. Most hydroxides are insoluble.
Exceptions:
Group IA hydroxides,
Ca(OH)2, Sr(OH)2, Ba(OH)2
Aqueous
Reactions
Exercise Using Solubility Rules
Classify these ionic compounds as soluble or insoluble in water: (a) sodium carbonate, Na2CO3, (b) lead sulfate, PbSO4.
Chemistry, The Central Science, 12th Edition © 2012 Pearson Education, Inc.
Theodore L. Brown; H. Eugene LeMay, Jr.; Bruce E. Bursten; Catherine J. Murphy; and Patrick Woodward
Metathesis (Exchange) 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:
AgNO3(aq) + KCl(aq)  AgCl(s) + KNO3(aq)
Aqueous
Reactions
Exercise 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 Chemistry
• It is helpful to pay attention to exactly what

species are present in a reaction mixture
(i.e., solid, liquid, gas, aqueous solution).
• If we need to understand reactivity, we must

be aware of just what is changing during the
course of a reaction.
Aqueous
Reactions
Molecular Equation
The molecular equation lists the reactants and
products in their molecular form:
AgNO3(aq) + KCl(aq)  AgCl(s) + KNO3(aq)
Aqueous
Reactions
Ionic Equation
• In the 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:
Ag+(aq) + NO3−(aq) + K+(aq) + Cl−(aq)  AgCl(s) + K+(aq) + NO3−(aq)
Aqueous
Reactions
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 only things left in the equation are those things
that change (i.e., react) during the course of the
reaction:
Ag+(aq) + Cl−(aq)  AgCl(s) Aqueous

Reactions
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 only things left in the equation are those things
that change (i.e., react) during the course of the
reaction.
• Those things that didn’t change (and were deleted
from the net ionic equation) are called spectator
ions:

Aqueous
Reactions
Writing Net Ionic Equations
1. Write a balanced molecular equation.
2. Dissociate all strong electrolytes.
3. Cross out anything that remains unchanged
from the left side to the right side of the
equation.
4. Write the net ionic equation with the species
that remain.
Aqueous
Reactions
Decide whether the following reaction occurs. If
? it does, write the molecular, ionic, and net ionic

equations.
KBr + MgSO4 
1. Determine the product formulas:

K+ and SO42− make K2SO4
Mg2+ and Br − make MgBr2
2. Determine whether the products are soluble:

K2SO4 is soluble
MgBr2 is soluble
KBr + MgSO4  no reaction
Decide whether the following reaction
? occurs. If it does, write the molecular,

ionic, and net ionic equations.
NaOH + MgCl2 
Na+ and Cl− make NaCl
Mg2+ and OH− make Mg(OH)2

NaCl is soluble
Mg(OH)2 is insoluble

Molecular Equation
(Balance the reaction and include state symbols)
2NaOH(aq) + MgCl2(aq) 
2NaCl(aq) + Mg(OH)2(s)
Ionic Equation
2Na+(aq) + 2OH−(aq) + Mg2+(aq) + 2Cl−(aq) 
2Na+(aq) + 2Cl−(aq) + Mg(OH)2(s)
Net Ionic Equation

2OH−(aq) + Mg2+(aq)  Mg(OH)2(s)
Decide whether the following reaction
? occurs. If it does, write the molecular,

ionic, and net ionic equations.
K3PO4 + CaCl2 
K+ and Cl− make KCl
Ca2+ and PO43− make Ca3(PO4)2

KCl is soluble
Ca3(PO4)2 is insoluble

Molecular Equation
2K3PO4(aq) + 3CaCl2(aq) 
6KCl(aq) + Ca3(PO4)2(s)
Ionic Equation
6K+(aq) + 2PO43−(aq) + 3Ca2+(aq) + 6Cl−(aq) 
6K+(aq) + 6Cl−(aq) + Ca3(PO4)2(s)
Net Ionic Equation

2PO43−(aq) + 3Ca2+(aq)  Ca3(PO4)2(s)
Types of Chemical Reactions
1. Precipitation reactions: a solid ionic

substance forms from the mixture of two
solutions of ionic substances.
2. Acid–base reactions: reactions that involve
the transfer of a proton (H+) between reactants.
3. Oxidation–reduction reactions: reactions that
involve the transfer of electrons between
reactants.

A precipitate is an insoluble solid compound
formed during a chemical reaction in solution.
Predicting Precipitation Reactions

1. Predict the products (exchange of parts).
2. Determine the state of each product: (s), (l),
(g), (aq).
3. If all products are aqueous (aq), no net
reaction occurred.
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4.3: Acids and bases
Arrhenius Acid
A substance that produces hydrogen ions, H+,
when it dissolves in water.
Arrhenius Base
A substance that produces hydroxide ions, OH−,
when it dissolves in water.

Brønsted–Lowry Acid
The species (molecule or ion) that donates a
proton to another species in a proton−transfer
reaction.
Brønsted–Lowry Base
The species (molecule or ion) that accepts a
proton from another species in a proton−transfer
reaction.
4 | 33
Strong Acid
An acid that ionizes completely in water. It is
present entirely as ions; it is a strong electrolyte.
Common strong acids:

HNO3 H2SO4 HClO4
HCl HBr HI
4 | 34
Weak Acid
An acid that only partly ionizes in water. It is
present primarily as molecules and partly as ions;
it is a weak electrolyte.
If an acid is not strong, it is weak.
4 | 35
In Figure A, a solution of In Figure B, a solution of
HCl (a strong acid) HF (a weak acid) also
illustrated on a illustrated on a
molecular/ionic level, molecular/ionic level,
shows the acid as all shows mostly molecules
ions. with very few ions.
4 | 36
Strong Base
A base that ionizes completely in water. It is
present entirely as ions; it is a strong electrolyte.
Common strong bases:

LiOH NaOH KOH
Ca(OH)2 Sr(OH)2 Ba(OH)2
4 | 37
Weak Base
A base that is only partly ionized in water. It is
present primarily as molecules and partly as ions;
it is a weak electrolyte. These are often nitrogen
bases such as NH3:
NH3(aq) + H2O(l)  NH4+(aq) + OH−(aq)
If a base is not strong, it is weak.

Classify the following as strong or
? weak acids or bases:

a. KOH
b. H2S
c. CH3NH2
d. HClO4
a. KOH is a strong base.
b. H2S is a weak acid.
c. CH3NH2 is a weak base.
d. HClO4 is a strong acid.
Neutralization Reaction
A reaction of an acid and a base that results in an
ionic compound (a salt) and possibly water.
4 | 40
?
Write the molecular, ionic, and net ionic
equations for the neutralization of
sulfurous acid, H2SO3, by potassium
hydroxide, KOH.

Molecular Equation
H2SO3(aq) + 2KOH(aq)  2H2O(l) + K2SO3(aq)
Ionic Equation
H2SO3(aq) + 2K+(aq) + 2OH−(aq) 
2H2O(l) + 2K+(aq) + SO32−(aq)
Net Ionic Equation

H2SO3(aq) + 2OH−(aq)  2H2O(l) + SO32−(aq)

Acid−base reactions with gas−formation
Sulfides, carbonates, sulfites react with acid to form a
gas.
Na2S(aq) + 2HCl(aq)  2NaCl(aq) + H2S(g)
Na2CO3(aq) + 2HCl(aq) 
2NaCl(aq) + H2O(l) + CO2(g)
Na2SO3(aq) + 2HCl(aq) 
2NaCl(aq) + H2O(l) + SO2(g)
4 | 43
? Write the molecular, ionic, and net ionic
equations for the reaction of copper(II)
carbonate with hydrochloric acid.

Molecular Equation
CuCO3(s) + 2HCl(aq) 
CuCl2(aq) + H2O(l) + CO2(g)
Ionic Equation
CuCO3(s) + 2H+(aq) + 2Cl−(aq) 
Cu2+(aq) + 2Cl−(aq) + H2O(l) + CO2(g)
Net Ionic Equation

CuCO3(s) + 2H+(aq)  Cu2+(aq) + H2O(l) + CO2(g)
4.4: Oxidation-Reduction Reactions
• An oxidation occurs when an atom or ion loses electrons.

• A reduction occurs when an atom or ion gains electrons.
• One cannot occur without the other.
Aqueous
Reactions
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.
Aqueous
Reactions
Rules for Assigning Oxidation Numbers
1. Elements: The oxidation number of an atom in
an element is zero.
2. Monatomic ions: The oxidation number of an
atom in a monatomic ion equals the charge on
the ion.
3. Oxygen: The oxidation number of oxygen is −2
in most of its compounds. (An exception is O in
H2O2 and other peroxides, where the oxidation
number is −1.)
4. Hydrogen: The oxidation number of hydrogen
is +1 in most of its compounds. (The oxidation
number of hydrogen is −1 in binary compounds
with a metal such as CaH2.)
4 | 48
5. Halogens: The oxidation number of fluorine is
−1. Each of the other halogens (Cl, Br, I) has
an oxidation number of −1 in binary
compounds, except when the other element is
another halogen above it in the periodic table
or the other element is oxygen.
6. Compounds and ions: The sum of the
oxidation numbers of the atoms in a compound
is zero. The sum of the oxidation numbers of
the atoms in a polyatomic ion equals the
charge on the ion.

Potassium permanganate, KMnO4, is a
? purple−colored compound; potassium

manganate, K2MnO4, is a
green−colored compound. Obtain the
oxidation numbers of the manganese in
these compounds.
K Mn O
1(+1) + 1(oxidation number of Mn) + 4(−2) = 0
1 + 1(oxidation number of Mn) + (−8) = 0
(−7) + (oxidation number of Mn) = 0
Oxidation number of Mn = +7
K Mn O
2(+1) + 1(oxidation number of Mn) + 4(−2) = 0
2 + 1(oxidation number of Mn) + (−8) = 0
(−6) + (oxidation number of Mn) = 0
Oxidation number of Mn = +6
In KMnO4, the oxidation number of Mn is +7.

In K2MnO4, the oxidation number of Mn is +6.
4 | 51
?
What is the oxidation number of Cr in
dichromate, Cr2O72−?
Cr O
2(oxidation number of Cr) + 7(−2) = −2
2(oxidation number of Cr) + (−14) = −2
2(oxidation number of Cr) = +12
Oxidation number of Cr = +6
4 | 52
Displacement Reactions
• In displacement reactions, ions oxidize an element.
• The ions, then, are reduced.
Aqueous
Reactions
In this reaction,
silver ions oxidize
copper metal:
Cu(s) + 2Ag+(aq)  Cu2+(aq) + 2Ag(s)

Aqueous
Reactions
The reverse reaction,

however, does not
occur:
x Cu(s) + 2Ag+(aq)
Cu2+(aq) + 2Ag(s) 
Aqueous
Reactions
Activity Series
Aqueous
Reactions
Exercise Determining When an Oxidation-Reduction
Reaction Can 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.
4.5: Concentrations of Solutions
Molarity
• Two solutions can contain the same compounds
but be quite different because the proportions of
those compounds are different.
• Molarity is one way to measure the concentration
of a solution:
moles of solute
Molarity (M) =
volume of solution in liters Aqueous
Reactions
Preparing a Solution
• To create a solution of a
known molarity, one weighs
out a known mass (and,
therefore, number of moles) of
the solute.
• The solute is added to a
volumetric flask, and solvent is
added to the line on the neck
of the flask.
Aqueous
Reactions
Exercise Calculating Molarity
Calculate the molarity of a solution made by dissolving

23.4 g of sodium sulfate (Na2SO4) in enough water to
form 125 mL of solution.
Exercise Calculating Molar Concentrations of Ions
What is the molar concentration of each ion present in a

0.025 M aqueous solution of calcium nitrate?
Exercise Using Molarity to Calculate Grams of Solute
How many grams of Na2SO4 are required to make 0.350

L of 0.500 M Na2SO4?
Dilution
• One can also dilute a more concentrated
solution by:
– Using a pipet to deliver a volume of the solution to a new
volumetric flask, and
– Adding solvent to the line on the neck of the new flask.
Aqueous
Reactions
Dilution
The molarity of the new solution can be determined
from the equation
Mc  Vc = Md  Vd
where Mc and Md are the molarity of the concentrated

and dilute solutions, respectively, and Vc and Vd are
the volumes of the two solutions.
Aqueous
Reactions
Exercise Preparing a Solution by Dilution
How many milliliters of 3.0 M H2SO4 are needed to make

450 mL of 0.10 M H2SO4?
4.6: Using Molarities in Stoichiometric
Calculations
Aqueous
Reactions
Exercise 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?
Titration
Titration is an
analytical
technique in
which one can
calculate the
concentration
of a solute in
a solution.
Aqueous
Reactions
Exercise 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, then remove
them 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?
Exercise 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)
The end point in this type of titration is marked by a change in

color of a special type of indicator. (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 percent Cl– does it contain?

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Chapter 4

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Chapter 4

Reactions In Aqueous Solutions

• The solvent is present in greatest abundance.

• All other substances are solutes.

A solvent such as water is needed to dissolve

A solvent such as hexane (C6H14) is needed to

Which of the following solutes will

1) Na2SO4 Yes, polar (ionic)

• Soluble ionic compounds tend to be

• A strong electrolyte dissociates completely

AgNO3(aq) + KCl(aq)  AgCl(s) + KNO3(aq)

• It is helpful to pay attention to exactly what

• If we need to understand reactivity, we must

AgNO3(aq) + KCl(aq)  AgCl(s) + KNO3(aq)

Ag+(aq) + NO3−(aq) + K+(aq) + Cl−(aq)  AgCl(s) + K+(aq) + NO3−(aq)

• To form the net ionic equation, cross out anything

Ag+(aq) + NO3−(aq) + K+(aq) + Cl−(aq)  AgCl(s) + K+(aq) + NO3−(aq)

Ag+(aq) + Cl−(aq)  AgCl(s) Aqueous

Ag+(aq) + NO3−(aq) + K+(aq) + Cl−(aq)  AgCl(s) + K+(aq) + NO3−(aq)

? it does, write the molecular, ionic, and net ionic

1. Determine the product formulas:

2. Determine whether the products are soluble:

? occurs. If it does, write the molecular,

2. Determine whether the products are soluble:

Copyright © Cengage Learning. All rights reserved. 4 | 26

Net Ionic Equation

? occurs. If it does, write the molecular,

2. Determine whether the products are soluble:

Copyright © Cengage Learning. All rights reserved. 4 | 28

Net Ionic Equation

1. Precipitation reactions: a solid ionic

Copyright © Cengage Learning. All rights reserved. 4 | 30

Predicting Precipitation Reactions

Copyright © Cengage Learning. All rights reserved. 4 | 32

Common strong acids:

If an acid is not strong, it is weak.

Common strong bases:

If a base is not strong, it is weak.

Copyright © Cengage Learning. All rights reserved. 4 | 38

? weak acids or bases:

Copyright © Cengage Learning. All rights reserved. 4 | 41

Net Ionic Equation

Copyright © Cengage Learning. All rights reserved. 4 | 42

Na2S(aq) + 2HCl(aq)  2NaCl(aq) + H2S(g)

Copyright © Cengage Learning. All rights reserved. 4 | 44

Net Ionic Equation

• An oxidation occurs when an atom or ion loses electrons.

Copyright © Cengage Learning. All rights reserved. 4 | 49

? purple−colored compound; potassium

In KMnO4, the oxidation number of Mn is +7.

Cu(s) + 2Ag+(aq)  Cu2+(aq) + 2Ag(s)

The reverse reaction,

Will an aqueous solution of iron(II) chloride oxidize

Calculate the molarity of a solution made by dissolving

What is the molar concentration of each ion present in a

How many grams of Na2SO4 are required to make 0.350

where Mc and Md are the molarity of the concentrated

How many milliliters of 3.0 M H2SO4 are needed to make

How many grams of Ca(OH)2 are needed to neutralize

One commercial method used to peel potatoes is to soak

The quantity of Cl– in a municipal water supply is determined by

The end point in this type of titration is marked by a change in

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