Principles and Modern Applications 8 th EDITION

Petrucci • Harwood • Herring

Chapter 5: Introduction to Reactions

in Aqueous Solutions

5
1
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

2
5.1 The Nature of Aqueous Solutions
•




• Aqueous



• solvent molecules

• Water solvent
• Solute particles-molecules or ions much smaller
number
3
Conduction Illustrated

• An important characteristic of an aqueous solution of ions is that it

conducts electricity, provided the concentration of ions is not too low.

• Electric current is a flow of charged particles.

• One type of current is electrons flowing through a
wire, from cathode (negative electrode) to anode
(positive electrode).

• Another type of current: anions and cations moving

through a solution as shown here. Cations move to the
cathode, anions move to the anode.
• An external source of potential (voltage) is required in
either case!
4
Electrolyte

• A substance, such as sodium chloride, that dissolved in water

and produces ions to give an electrically conducting solution is
called an electrolyte.

• A substance, such as sucrose, (C12H22O11), that is not ionized

and does not conduct electric current when dissolved in water is
called a Nonelectrolyte.

5
Types of Electrolytes

strong electrolyte
• ions
• good conductors.

nonelectrolyte
• molecules
• do not conduct electricity.

weak electrolyte
• poor conductors.
•

6
Classification Scheme for Solutes

7
Three Types of Electrolytes

CH3OH MgCl2 CH3COOH

entirely as individual ions

a small fraction of the molecules ionize

8
Generalization for 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 strong electrolyte:

A weak electrolyte:

A non-electrolyte:

9
Is it a strong electrolyte, a weak electrolyte,
or a nonelectrolyte?

•
•
•
How do we tell
whether an acid
• (or base) is weak?

• Nonelectrolytes include:
• Most molecular compounds
• Most organic compounds (most of them are molecular)
10
Electrolyte Classification of Some Common Substances

Strong Electrolytes Weak Electrolytes Nonelectrolytes ______

HCl, HBr, HI CH3COOH H2 O
HClO4 HF CH3OH
HNO3 C2H5OH
H2SO4 C12H22O11(sucrose)
KBr Most organic compounds
NaCl
NaOH, KOH
Other soluble
ionic compounds ______

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• water soluble MgCl2(s)

MgCl2(aq) → Mg2+(aq) + 2 Cl-(aq)

• Hydrogen chloride, HCl,

HCl(aq) → H+(aq) + Cl-(aq)

• CH3COOH(aq)

CH3COOH(aq) CH3COO-(aq) + H+(aq)

12
Ion Concentrations in Solution

Trick” question …

Na2SO4
0.010 mol Na2SO4 1.00 L

The answer is:

… zero …

WHY??

13
Calculating Ion Concentrations in Solution

Na2SO4(aq) → 2Na2+(aq) + SO42-(aq)

0.010 M Na2SO4:
 2 moles of Na+
[Na+] = 0.020 M.
 1 mole of SO42–
[SO42–] = 0.010 M.
 [Na2SO4]= 0

one
two more sources.
14
Relative Concentrations 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

15
16
Aqueous Reactions

• Aqueous reactions can be grouped into three general categories.

1. Precipitation Reactions
2. Acid-Base Neutralization Reactions
3. Reduction-Oxidation (Redox) Reactions

17
Reactions that Form Precipitates

insoluble

soluble
not soluble

precipitate

cations anions
precipitate.
18
5-2 Precipitation Reactions
• Soluble ions can combine to form an insoluble compound
(precipitate).

• One laboratory use of precipitation reactions is in identifying the

ions present in a solution.

• A test for the presence of chloride ion in water.

Ag+(aq) + Cl-(aq) → AgCl(s)

Qualitative test for Cl- in tap water

• In industry, precipitation reactions are used in the manufacture of

numerous chemicals.

• In the extraction of magnesium metal from seawater, for instance,

the first step is to precipitate Mg2+ as Mg(OH)2(s).
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Net Ionic Equations
• Reaction of silver nitrate and sodium iodide in an aqueous solution yields
sodium nitrate in solution and a pale yellow precipitate of silver iodide.
• We can write the equation for the reaction as follow:

whole formula form:

AgNO3(aq) + NaI(aq) → AgI(s) + NaNO3(aq)

ionic form: Spectator ions

Ag+(aq) + NO3-(aq) + Na+(aq) + I-(aq) → AgI(s)

AgI(s) + Na+(aq) + NO3-(aq)

Net ionic equation: Ag+(aq) + I-(aq) → AgI(s)

20
Precipitate of silver iodide

AgNO3(aq) NaI(aq) AgI(s)

Na+(aq) NO3-(aq)

• AgNO3 (a) NaI (b)

AgI(s) (c)
21
Predicting Precipitation Reactions

AgNO3(aq) + KBr(aq) → ?

Ag+(aq) + NO3-(aq) + K+(aq) + Br-(aq) → ?

• two possibilities

a precipitate-
 no reaction.

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23
•
AgBr(s) is insoluble, whereas KNO3 is soluble.

• Ionic equation

Ag+(aq) + NO3-(aq) + K+(aq) + Br-(aq) → AgBr(s) + K+(aq) + NO3-(aq)

• Net ionic equation:

Ag+(aq) + Br-(aq) → AgBr(s)

24
•
•

25
26
Verifying the predictions made in Example 5-2
(a) When NaOH(aq) is added to MgCl2(aq), a white precipitate of Mg(OH) 2(s)
forms.

(b) When colorless BaS(aq) is added to blue CuSO4(aq), a dark precipitate

forms. The precipitate is a mixture of white BaSO4(s) and black CuS(s). (A
slight excess of CuSO4 remains in solution.)

(c) No reaction occurs when colorless (NH4) 2SO4(aq) is added to colorless

ZnCl2(aq).

(a) (b) (c)

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5-3 Acid-Base Reactions

• acidus
•

• al-qali
•
An acid, a base, and an acid–base indicator

•
•
•

28
Acids
Arrhenius provide H+

HCl(aq) → H+(aq) + Cl-(aq)

CH3COOH(aq) ←
→ H+(aq) + CH3COO-(aq)
Only some of the CH3COOH molecules are converted into H+
and CH3COO- ions.

proton donors

29
 proton donors

HCl(aq) + H2O (l) ↔ H3O+(aq) + Cl–(aq)

CH3COOH(aq) + H2O (l) ↔ H3O+(aq) + CH3COO–(aq)

30
Bases

Arrhenius

NaOH(aq) → Na+(aq) + OH-(aq)

H2O

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

NH3

proton acceptors

31
 proton acceptors

NH3 (aq) + H2O (l) ↔ NH4+ (aq) + OH– (aq)

32
Acidic and Basic Solutions

• Small numbers of H+ and OH- ions are present even in pure water.

• In pure water the following reaction occurs:

H2O(l) ↔ H+ (aq) + OH– (aq)

• Measurments show that [H+]water = [OH-]water = 1.0 x 10-7 M °

[H+] > [H+]water

[OH-] > [OH-]water

33
Reactions of Acids and Bases:
Strong and Weak Acids

• Strong acids

No HCl in solution,
only H+ and Cl– ions.

• Weak acids are weak electrolytes. Some of the dissolved molecules

ionize; the rest remain as molecules.
In water: CH3COOH(l) ←
→ H+(aq) + CH3COO–(aq)
Just a little H+ forms.

• Some acids have more than one ionizable hydrogen atom.

They ionize in “steps” (more in Chapter 15).
H2SO4 → H+ + HSO4–
HSO4– ←
→ H+ + SO42–
34
Strong and Weak Bases

• Strong bases

• Weak bases:
different.
• form

←
→
←
→

Just a little OH– forms.

Most of the weak base remains
in the molecular form.

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36
Acid–Base Reactions: Neutralization

Neutralization

water salt

37
Acid–Base Reactions: Net Ionic Equations
HCl(aq) + NaOH(aq)  H2O(l) + NaCl(aq)
(Acid) + (base) → (water) + (salt)

Na+ and Cl–

ions are spectator
ions.

H+ + Cl– + Na+ + OH–  H2O + Na+ + Cl–

H+ (aq) + OH– (aq)  H2O (aq)

H+ + Cl– + NH3  NH4+ + Cl–

H+ (aq) + NH3 (aq)  NH4+ (aq)

A net ionic equation shows the species actually involved in the reaction.
38
Recognizing Acids and Bases

ionizable


39
More Acid-Base Reactions

•
OH–

• The reaction of Mg(OH)2(s) with a strong acid

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

• The reaction of Mg(OH)2(s) with a weak acid

Mg(OH)2(s) + 2 CH3CO2H(aq) →

Mg2+(aq) + 2 CH3CO2-(aq) + 2 H2O(l)

40
More Acid-Base Reactions
• CaCO3(s).

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

But: H2CO3(aq) → H2O(l) + CO2(g)

decomposes

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

base acid

41
42
 5-4 Oxidation-Reduction Reactions:
Some General Principles
•
D
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.

• gains O oxidation.
loses O reduction.

Oxidation- Reduction Redox reaction

43
Oxidation State Changes

•
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.

44
 Fe2O3(s) + 2 Al(s)  Al2O3(s) + 2 Fe(l)

Figure 5-11
Thermite Reaction

45
46
Oxidation and Reduction Half-Reactions

• An oxidation-reduction reaction

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

•
oxidation a reduction
47
Oxidation: Zn(s) → Zn2+(aq) + 2 e-

Reduction: Cu2+(aq) + 2 e- → Cu(s)

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

48
Oxidation and Reduction

Oxidation
• increases
• Electrons on the right

Reduction
• decreases
• Electrons on the left

• total number of electrons oxidation

total number of electrons reduction.

49
50
5-5 Balancing Oxidation-Reduction Equations

51
The Half-Equation Method

oxidation reduction

the same number

of electrons appear in each half-equation.

52
53
54
55
56
57
58
Disproportionation Reactions

and

2 H2O2(aq)  H2O(l) + O2(g)

Oxidation: 2 S2O32-(aq) + H2O(l)  2SO2(g) + 2H+(aq) + 4e

Reduction: 2 S2O32-(aq) + 6H+(aq) + 4e  2S(s) + H2O(l)

Overall: 2 S2O32-(aq) + 2H+(aq)  S(s) + SO2(g) + H2O(l)

59
5-6 Oxidizing and Reducing Agents

An oxidizing agent (oxidant)


 oxidation state decreases in a redox reaction
 gains electrons (electrons are found on the left side of its half-equation)


A reducing agent (reductant)


 oxidation state increases in a redox reaction
 loses electrons (electrons are found on the right side of its half-equation)


60
 Oxidation states of nitrogen:
Identifying oxidizing and reducing agents

• NO3- N 2 O4 highest oxidation states (O.S)

oxidizing agents

• N 2 H4 NH3 lowest oxidation states

reducing agents.

61
• Ozone, a triatomic form of oxygen, is an oxidizing agent used in water
purification, as in the oxidation of the organic compound phenol.

• Thiosulfate ion, is an important reducing agent. One of its industrial uses is

as an antichlor to destroy residual chlorine from the bleaching of fibers.
63
5-7 Stoichiometry of Reactions in Aqueous Solutions:
Titrations
titration
stoichiometric proportion.

the number of moles the

number of grams the percentage the concentration analyte

one reactant titrant a buret other

reactant a flask an indicator.
Indicators

endpoint
Equivalence Point
64
An Acid–Base Titration
Titrant

Equivalence Point

Indicator

Analyte

5.0 mL CH3CO2H A few drops Add 0.1000 M NaOH The “endpoint”

phenolpthalein (close to the equivalence point)

65
66
 Standardization Solutions
•

•
the solid KMnO4(s) is not pure
•

• standardization of a solution

67
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