Chemistry 140 Fall 2002

Petrucci’s General Chemistry

P R I N C I P L E S A N D M O D E R N A P P L I C AT I O N S
Twelfth Edition

PETRUCCI HERRING MADURA BISSONNETTE

5
Introduction to
Reactions in Aqueous
Solutions

Introduction to Reactions CONTENTS

in Aqueous Solutions 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

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Chemistry 140 Fall 2002

5.1 The Nature of Aqueous Solutions

Water
Inexpensive
Can dissolve a vast number of substances
Many substances dissociate into ions

Aqueous solutions are found everywhere

Seawater
Living systems

5.1 The Nature of Aqueous Solutions

Strong electrolyte is completely ionized.

Good electrical conduction.

Weak electrolyte only partially ionizes.

Fair conductor of electricity.

Non-electrolyte does not dissociate.

Poor conductor of electricity.

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Chemistry 140 Fall 2002

FIGURE 5-2
Conduction of electricity through a solution

FIGURE 5-3
A classification scheme for solutes

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Chemistry 140 Fall 2002

FIGURE 5-4
Three Types of Electrolytes

 Essentially all soluble ionic compounds and only a relatively few molecular
compounds are strong electrolytes.
 Most molecular compounds are either nonelectrolytes or weak electrolytes.

A non-electrolyte:
CH3OH(aq)

A strong electrolyte:
MgCl2(s) Mg2+(aq) + 2 Cl−(aq)

A weak electrolyte:
CH3CO2H(aq) CH3CO2−(aq) + H+(aq)

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Chemistry 140 Fall 2002

Dissociation and Ionization

FIGURE 5-5
An ionic compound dissolving in water

FIGURE 5-6
The hydrated proton

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Chemistry 140 Fall 2002

A Notation for Representing

Concentrations of Entities in Solution
MgCl2(s) → Mg2+(aq) + 2 Cl −(aq)

In 0.0050 M MgCl2:

Stoichiometry is important.

[Mg2+] = 0.0050 M [Cl−] = 0.0100 M [MgCl2] = 0 M

5-2 Precipitation Reactions

Soluble ions can combine to
form an insoluble compound.
Precipitation occurs.

A test for the presence of

chloride ion in water.

Ag+(aq) + Cl−(aq) → AgCl(s)

FIGURE 5-7
Qualitative test for Cl− in tap water

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Chemistry 140 Fall 2002

Net Ionic Equations

“whole formula” form:
AgNO3(aq) +NaI(aq) → AgI(s) + NaNO3(aq)

“ionic” form:
Ag+(aq) + NO3 −(aq) + Na+(aq) + I −(aq) → AgI(s) + Na+(aq) + NO3−(aq)

Spectator ions
Net ionic equation:
Ag+(aq) + I −(aq) → AgI(s)

Predicting Precipitation Reactions

FIGURE 5-8
A precipitate of silver iodide

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Chemistry 140 Fall 2002

5-3 Acid-Base Reactions

Acid from Latin acidus

Sour taste
Alkalai from Arabic al-qali
Bitter taste
Acid-Base theory
Svante Arrhenius 1884
Brønsted and Lowry 1923

FIGURE 5-10
An acid, a base, and an acid–base indicator

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Chemistry 140 Fall 2002

Acids
Brønsted Lowry acids provide H+ in aqueous solution.

Strong acids completely ionize:

HCl(aq) → H+(aq) + Cl–(aq)

Weak acid ionization is not complete:

CH3CO2H(aq) ←
→ H+(aq) + CH3CO2–(aq)

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Chemistry 140 Fall 2002

Bases
Bases provide OH− in aqueous solution.

Strong bases:

NaOH(aq) →
HO
2
Na+(aq) + OH–(aq)
Weak bases:

NH3(aq) + H2O(l) ←
→ OH–(aq) + NH4+(aq)

Brønsted Lowry bases are proton acceptors.

Acidic and Basic Solutions

H2O (l) H+(aq) + OH– (aq)

[H+] water = [OH–] water = 1.0 ×10–7 (25°C)

An acidic solution has [H+] > [H+]water

A basic solution has [OH–] > [OH–]water

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Chemistry 140 Fall 2002

Neutralization
HCl (aq) +NaOH (aq) NaCl (aq) + H2O (l)
acid base salt water

ionic form
H+(aq) + Cl–(aq) + Na+(aq) + OH–(aq) Na+(aq) + Cl–(aq) + H2O (l)

acid base salt water

Net ionic equation

H+ (aq) + HO– (aq) H2O (l)

CH3CO2H (aq) +NaOH (aq) CH3CO2Na (aq) + H2O (l)

acid base salt water

ionic form
CH3CO2H (aq) + Na+(aq) + OH–(aq) Na+(aq) + CH3CO2–(aq) + H2O (l)

acid base salt water

Net ionic equation

CH3CO2H (aq) + HO– (aq) CH3CO2– (aq) + H2O (l)

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Chemistry 140 Fall 2002

Recognizing Acids and Bases

Acids contain ionizable hydrogen atoms.
HC2H3O2 or CH3CO2H

acetic acid

CH4 is not an acid

NH3 is a weak base
CH3CH2OH is not a base

CH3CH2OH (aq) CH3CH2+ (aq) + OH– (aq)

More Acid-Base Reactions

Milk of magnesia Mg(OH)2

Mg(OH)2 (s) + 2 H+(aq) → Mg2+ (aq) + 2 H2O (l)

Mg(OH)2 (s) + 2 CH3CO2H (aq) →

Mg2+(aq) + 2 CH3CO2 −(aq) + 2 H2O(l)

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Chemistry 140 Fall 2002

More Acid-Base Reactions

Limestone and marble.

CaCO3(s) + 2 H+(aq) → Ca2+(aq) + H2CO3(aq)

But: H2CO3(aq) → H2O(l) + CO2(g)

CaCO3(s) + 2 H+(aq) → Ca2+(aq) + H2O(l) + CO2(g)

FIGURE 5-11
Damage caused by acid rain

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Chemistry 140 Fall 2002

5-4 Oxidation-Reduction Reactions:

Some General Principles

Hematite is converted to iron in a blast furnace.

D
Fe2O3(s) + 3 CO(g) → 2 Fe(l) + 3 CO2(g)

Oxidation and reduction always occur together.

Fe3+ is reduced to metallic iron.
CO(g) is oxidized to carbon dioxide.

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Chemistry 140 Fall 2002

Oxidation State Changes

Assign oxidation states:

+3 –2 +2 –2 0 +4 –2
D
Fe2O3(s) + 3 CO(g) → 2 Fe(l) + 3 CO2(g)

Fe3+ is reduced to metallic iron.

CO(g) is oxidized to carbon dioxide.

Fe2O3(s) + 2 Al(s)  Al2O3(s) + 2 Fe(l)

FIGURE 5-12
Thermite Reaction

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Chemistry 140 Fall 2002

Oxidation and Reduction Half-Reactions

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

FIGURE 5-13
An oxidation-reduction reaction

The reaction represented by two half-reactions.

Oxidation: Zn (s) → Zn2+ (aq) + 2 e−

Reduction: Cu2+ (aq) + 2 e− → Cu (s)

Overall: Cu2+ (aq) + Zn (s) → Cu (s) + Zn2+ (aq)

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Chemistry 140 Fall 2002

Oxidation
O.S. of some element increases in the reaction.
Electrons are on the right of the equation

Reduction
O.S. of some element decreases in the reaction.
Electrons are on the left of the equation.

5-5 Balancing Oxidation-Reduction

Equations

Few can be balanced by inspection.

Systematic approach required.

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Chemistry 140 Fall 2002

The Half-Equation Method

• 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

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Chemistry 140 Fall 2002

Balancing Redox Equations

in a Basic Solution

Disproportionation Reactions
The same substance is both oxidized and reduced.
Some have practical significance

Hydrogen peroxide
2 H2O2(aq) 2 H2O(l) + O2(g)

Sodium thiosulphate
2 S2O3– (aq) + 2 H+(aq) S (s) + SO2 (g) + H2O (l)

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Chemistry 140 Fall 2002

FIGURE 5-15
Antiseptic action of hydrogen peroxide solution

5-6 Oxidizing and Reducing Agents.

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

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Chemistry 140 Fall 2002

5-6 Oxidizing and Reducing Agents.

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

FIGURE 5-16
Oxidation states of nitrogen: Identifying oxidizing and reducing agents

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Chemistry 140 Fall 2002

N2O4 (l) + 2 N2H4 (l) 3 N2 (g) + 4 H2O (g)

2 N2H4 (l) + H2 (g) 3 NH3 (g)

C6H5OH (aq) + 14 O3 (g) 6 CO2 (g) + 3 H2O (l) + 14 O2 (g)

S2O32– (aq) + 4 Cl2 (g) + 5 H2O (l) 2 HSO4– (aq) + 8 H+ (aq) + 8 Cl– (aq)

FIGURE 5-17
Bleaching action of NaOCl(aq)

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Chemistry 140 Fall 2002

5-7 Stoichiometry of Reactions in

Aqueous Solutions: Titrations

FIGURE 5-18
An acid–base titration—Example 5-9 illustrated

FIGURE 5-19
Standardizing a solution of an oxidizing agent through a redox
titration—Example 5-10 illustrated

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