Chapter 4 Introduction to Reactions in

Aqueous Solutions

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

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 5.1 The Nature of Aqueous Solutions

Molecular view of water and an aqueous solution of air

(a) Water molecules (red and white) are in close proximity in liquid
water.
(b) (b) Dissolved oxygen (red) and nitrogen (blue) molecules are far
apart, separated by water molecules.
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 Electrolytes
• Some solutes can
dissociate into ions.
• Electric charge can be
carried.

Conduction of electricity through a solution

Two graphite rods called electrodes are placed in a solution. The external source of electricity pulls
electrons from one rod and forces them onto the other rod, 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, electric charge is carried through the solution by the migration of ions.

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 Types of Electrolytes

• Strong electrolyte dissociates completely.

– Good electrical conduction.

• Weak electrolyte partially dissociates.

– Fair conductor of electricity.
• Non-electrolyte does not dissociate.
– Poor conductor of electricity.

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 Representation of Electrolytes using
Chemical Equations

A strong electrolyte:
MgCl2(s) → Mg2+(aq) + 2 Cl-(aq)
A weak electrolyte:
→ CH3CO2-(aq) + H+(aq)
CH3CO2H(aq) ←

A non-electrolyte:
CH3OH(aq)

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 Dissociation and Ionization

Methanol MgCl2 CH3COOH

(a) There are no ions present to speak of—only molecules. Methanol (methyl alcohol), is a
nonelectrolyte in aqueous solutions. Because a nonelectrolyte does not ionize in solution, a
solution of CH3OH is best represented as CH3OH(aq).
(b) The solute, MgCl2, is present almost entirely as individual ions. is a strong electrolyte in aqueous
solutions.
(c) A small fraction of the molecules ionize. is a weak electrolyte in aqueous solution. The molecules
that ionize produce acetate ions and ions, and the ions attach themselves to water molecules to form
hydronium ions, H3O+.

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 Ionization

that a molecule containing the –COOH group is a carboxylic acid. When a

carboxylic acid ionizes, it is the bond between the H and O atoms of the –
COOH group that ionizes.

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 Notation for Concentration

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

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Example 5-1
Calculating Ion concentrations in a Solution of a Strong
Electolyte.
What are the aluminum and sulfate ion concentrations in
0.0165 M Al2(SO4)3?.

Balanced Chemical Equation:

Al2(SO4)3 (s) → 2 Al3+(aq) + 3 SO42-(aq)

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Example 5-1

Aluminum Concentration:

0.0165 mol Al2(SO4)3 2 mol Al3+

[Al] = × = 0.0330 M Al3+
1L 1 mol Al2(SO4)3

Sulfate Concentration:

0.0165 mol Al2(SO4)3 3 mol SO42-

[SO42-] = × = 0.0495 M SO42-
1L 1 mol Al2(SO4)3

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 5-2 Precipitation Reactions

• Soluble ions can combine

to form an insoluble
compound.
• Precipitation occurs.

Ag+(aq) + Cl-(aq) → AgCl(s)

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 Net Ionic Equation
Overall Precipitation Reaction:
AgNO3(aq) +NaI (aq) → AgI(s) + NaNO3(aq)

Complete ionic equation:

Spectator ions
Ag+(aq) + NO3-(aq) + Na+(aq) + I-(aq) →
AgI(s) + Na+(aq) + NO3-(aq)
Net ionic equation:
Ag+(aq) + I-(aq) → AgI(s)

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 Solubility Rules

• Compounds that are soluble:

– Alkali metal ion and ammonium ion salts

Li+, Na+, K+, Rb+, Cs+ NH4+

– Nitrates, perchlorates and acetates

NO3- ClO4- CH3CO2-

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 Solubility Rules

• Compounds that are mostly soluble:

– Chlorides, bromides and iodides Cl-, Br-, I-
• Except those of Pb2+, Ag+, and Hg22+.
– Sulfates SO42-
• Except those of Sr2+, Ba2+, Pb2+ and Hg22+.
• Ca(SO4) is slightly soluble.

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 Solubility Rules

• Compounds that are insoluble:

– Hydroxides and sulfides HO-, S2-
• Except alkali metal and ammonium salts
• Sulfides of alkaline earths are soluble
• Hydroxides of Sr2+ and Ca2+ are slightly soluble.
– Carbonates and phosphates CO32-, PO43-
• Except alkali metal and ammonium salts

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 5-3 Acid-Base Reactions

• Latin acidus (sour)

– Sour taste
• Arabic al-qali (ashes of certain plants)
– Bitter taste

• Svante Arrhenius 1884 Acid-Base theory.

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 Acids
• Acids provide H+ in aqueous solution.

• Strong acids:

HCl(aq) → H+(aq) + Cl-(aq)

• Weak acids:
CH3CO2H(aq) ←
→ H+(aq) + CH3CO2-(aq)

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 Bases

• Bases provide OH- in aqueous solution.

• Strong bases:
NaOH(aq) → Na+(aq) + OH-(aq)
H2O

• Weak bases:
NH3(aq) + H2O(l) ←
→ OH-(aq) + NH4+(aq)

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 Acidic and Basic Solutions
Experiment shows small numbers of ions are present
even in pure water.

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 Neutralization
In a neutralization reaction, an acid and a base react to form an aqueous solution of
an ionic compound called a salt.

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:

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 Neutralization
The situation is different when either the acid or the base in a neutralization reaction is
weak. For example, consider the neutralization reaction between CH3COOH, a weak
acid, and NaOH:

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 Recognizing Acids and Bases.

• Acids have ionizable hydrogen ions.

– CH3CO2H or HC2H3O2

• Bases have OH- combined with a metal ion.

KOH

or are identified by chemical equations

Na2CO3(s) + H2O(l)→ HCO3-(aq) + 2 Na+(aq) + OH-(aq)

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 More Acid-Base Reactions

• Milk of magnesia Mg(OH)2

•The net ionic equation for strong acid
Mg(OH)2(s) + 2 H+(aq) → Mg2+(aq) + 2 H2O(l)

The net ionic equation for weak acid

Mg(OH)2(s) + 2 CH3CO2H(aq) →
Mg2+(aq) + 2 CH3CO2-(aq) + 2 H2O(l)

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 More Acid-Base Reactions

• Limestone and marble.

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

But: H2CO3(aq) → H2O(l) + CO2(g)

The net ionic equation for strong acid

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

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Some Commom Gas-forming Reactions

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 5-4 Oxidation-Reduction: Some
General Principles
• Hematite is converted to iron in a blast furnace.

Fe2O3(s) + 3 CO(g) → 22 Fe(l)
Fe(l) +
+ 33 CO
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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 Rules for Oxidation States

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 Oxidation State Changes

• Assign oxidation states:

3+ 2- 2+ 2- 0 4+ 2-

Fe2O3(s) + 3 CO(g) → 2 Fe(l) + 3 CO2(g)

Fe3+ is reduced to metallic iron.

CO(g) is oxidized to carbon dioxide.

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 Oxidation and Reduction

• 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.

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 Zinc in Copper Sulfate

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

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 Half-Reactions

• Represent a reaction 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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Balancing Oxidation-Reduction Equations

• Few can be balanced by inspection.

• Systematic approach required.
• The Half-Reaction (Ion-Electron) Method
• we focus equally on three factors:
• (1) the number of atoms of each type,
• (2) the number of electrons transferred,
• (3) the total charges on reactants and products.

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 Balancing in Acid
• Write the equations for the half-reactions.
– Balance all atoms except H and O.
– Balance oxygen using H2O.
– Balance hydrogen using H+.
– Balance charge using e-.
• Equalize the number of electrons.
• Add the half reactions.
• Check the balance.

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Example 5-6
Balancing the Equation for a Redox Reaction in Acidic Solution.
The reaction described below is used to determine the sulfite ion
concentration present in wastewater from a papermaking plant.
Write the balanced equation for this reaction in acidic solution..

SO32-(aq) + MnO4-(aq) → SO42-(aq) + Mn2+(aq)

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Example 5-6
Determine the oxidation states:
4+ 7+ 6+ 2+
SO32-(aq) + MnO4-(aq) → SO42-(aq) + Mn2+(aq)

Write the half-reactions:

SO32-(aq) → SO42-(aq) + 2 e-(aq)

5 e-(aq) +MnO4-(aq) → Mn2+(aq)

Balance atoms other than H and O:

Already balanced for elements.

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Example 5-6
Balance O by adding H2O:

H2O(l) + SO32-(aq) → SO42-(aq) + 2 e-(aq)

5 e-(aq) +MnO4-(aq) → Mn2+(aq) + 4 H2O(l)

Balance hydrogen by adding H+:

H2O(l) + SO32-(aq) → SO42-(aq) + 2 e-(aq) + 2 H+(aq)

8 H+(aq) + 5 e-(aq) +MnO4-(aq) → Mn2+(aq) + 4 H2O(l)

Check that the charges are balanced: Add e- if necessary.

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Example 5-6
Multiply the half-reactions to balance all e-:

5 H2O(l) + 5 SO32-(aq) → 5 SO42-(aq) + 10 e-(aq) + 10 H+(aq)

16 H+(aq) + 10 e-(aq) + 2 MnO4-(aq) → 2 Mn2+(aq) + 8 H2O(l)

Add both equations and simplify:

5 SO32-(aq) + 2 MnO4-(aq) + 6H+(aq) →

5 SO42-(aq) + 2 Mn2+(aq) + 3 H2O(l)

Check the balance!

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 Balancing in Basic Solution

• OH- appears instead of H+.

• Treat the equation as if it were in acid.

– Then add OH- to each side to neutralize H+.
– Remove H2O appearing on both sides of equation.
• Check the balance.

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 Disproportionation Reactions
In some oxidation–reduction reactions, called disproportionation reactions, the
same substance is both oxidized and reduced.

The oxidation state of oxygen changes from -1 in H2O2 to -2 in H2O (a

reduction)
The oxidation state of oxygen changes from 0 in O2 (an oxidation). That is,
both oxidized and reduced.
Another example is the disproportionation of in acid solution:

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 5-6 Oxidizing and Reducing Agents.

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 Redox

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Example 5-8
Identifying Oxidizing and Reducing Agents.
Hydrogen peroxide, H2O2, 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 or reducing agent.

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Example 5-8

H2O2(aq) + 2 Fe2+(aq) + 2 H+ → 2 H2O(l) + 2 Fe3+(aq)

Iron is oxidized, and so reducing agent and

peroxide is reduced, and so oxidation agent.

5 H2O2(aq) + 2 MnO4-(aq) + 6 H+ →
8 H2O(l) + 2 Mn2+(aq) + 5 O2(g)

Manganese is reduced, so oxidating agent and peroxide

is oxidized, so reducing agent.

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 5-7 Stoichiometry of Reactions in
Aqueous Solutions: Titrations.
• Titration
– Carefully controlled addition of one solution to
another.
• Equivalence Point
– Both reactants have reacted completely.
• Indicators
– Substances which change colour near an
equivalence point.

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 Indicators

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Example 5-10
Standardizing a Solution for Use in Redox Titrations.
A piece of iron wire weighing 0.1568 g is converted to Fe2+(aq)
and requires 26.42 mL of a KMnO4(aq) solution for its titration.
What is the molarity of the KMnO4(aq)?

5 Fe2+(aq) + MnO4-(aq) + 8 H+(aq) →

4 H2O(l) + 5 Fe3+(aq) + Mn2+(aq)

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Example 5-10
5 Fe2+(aq) + MnO4-(aq) + 8 H+(aq) → 4 H2O(l) + 5 Fe3+(aq) + Mn2+(aq)
Determine KMnO4 consumed in the reaction:

1 mol Fe 1 mol Fe2+

nKMnO 4 = 0.1568 g Fe   
55.847 g Fe 1 mol Fe
−
1 mol MnO4 1 mol KMnO4 −4
2+
 −
= 5.615  10 mol KMnO4
5 mol Fe 1 mol MnO4

Determine the concentration:

5.615  10 −4 mol KMnO4

[ KMnO4 ] = = 0.02140 M KMnO4
0.02624 L

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