Chemistry and Chemical Reactivity, Sixth Edition John C. Kotz, Paul M. Treichel, Gabriela C. Weaver

Tutorials

Active Figures

Additional Resources

1
Matter and
Measurement

• Screen 1.5: Mixtures
and Pure Substances
• Screen 1.12: Chemical
Changes

•
•
•
•

• 1.1: Classifying Matter
• 1.2: States of Matter–Solid, Liquid, and
Gas
• 1.3: Levels of Matter
• 1.15: Comparison of Farenheit, Celsius,
and Kelvin Scales

• Screen 1.6: Separation of
Mixtures
• Screen 1.7: Elements and

Atoms
• Screen 1.13: Chemical Change
on the Molecular Scale

2
Atoms and
Elements

• Screen 2.6: Electrons
• Screen 2.8: Protons
• Screen 2.10: The
Nucleus of the Atom
• Screen 2.16: The
Periodic Table

• Screen 2.11: Summary of Atomic
Composition
• Screen 2.14: The Mole
• Screen 2.15: Moles and Molar Mass of
the Elements

• 2.3: Measuring the Electron’s Charge to
Mass Ratio
• 2.6: Rutherford’s Experiment to
Determine the Structure of the Atom
• 2.8: Mass Spectrometer
• 2.10: Some of the 113 Known Elements

•
•

•
•

• 3.1: Reaction of the Elements
Aluminum and Bromine
• 3.4: Ways of Depicting the Methane
(CH4) Molecule
• 3.6: Ions
• 3.8: Common Ionic Compounds Based
on Polyatomic Ions
• 3.10: Coulomb’s Law and Electrostatic
Forces
• 3.17: Dehydrating Hydrating Cobalt(II)
Chloride, CoCl2 · 6H2O

• Screen 3.13: Alkanes
3
Molecules,
• Screen 3.19: Hydrated
Ions, and Their
Compounds
Compounds

•
•
•
•
•
•
4

Chemical
Equations and
Stoichiometry

Screen 1.10: Density
Screen 1.15: Temperature
Screen 1.16: The Metric System
Screen 1.17: Using Numerical
Information

Screen 3.5: Ions
Screen 3.6: Polyatomic Ions
Screen 3.10: Naming Ionic Compounds
Screen 3.12: Binary Compounds of the
Nonmetals
Screen 3.14: Compounds, Molecules,
and the Mole
Screen 3.15: Using Molar Mass
Screen 3.16: Percent Composition
Screen 3.17: Determining Empirical
Formulas
Screen 3.18: Determining Molecular
Formulas
Screen 3.19: Hydrated Compounds

• Screen 4.3: The Law of • Screen 4.4: Balancing Chemical
Conservation of Mass
Equations
• Screen 4.5: Weight
• Screen 4.6: Calculations in

Relations in Chemical
Stoichiometry
Reactions
• Screen 4.9: Percent Yield
• Screen 4.8: Limiting
Reactants

• Screen 3.8: Ionic Compounds
• Screen 3.13: Alkanes
• Screen 3.14: Compounds,
Molecules, and the Mole

• 4.2: The Reaction of Iron and Chlorine • Screen 4.5 Weight Relations in
Chemical Reactions
• 4.4: Oxidation of Ammonia
• 4.8: Analysis for the Sulfate Content of a • Screen 4.7: Reactions
Controlled by the Supply of
Sample
One Reactant
• 4.9: Combustion Analysis of a
• Screen 4.8: Limiting Reactants
Hydrocarbon

/>
Exercises

The Media Integration Guide on the next several pages provides you with
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i

Media Integration Guide

Chapter


ii

Media Integration Guide

Chapter

Exercises

Tutorials

Active Figures

Additional Resources

5
Reactions in
Aqueous Solution

• Screen 5.13: Oxidation
Numbers
• Screen 5.14: Recognizing
Oxidation–Reduction
Reactions

• Screen 5.16: Preparing
Solutions of Known
Concentrations
• Screen 5.18:
Stoichiometry of
Reactions in Solution

• Screen 5.4: Solubility of Ionic
Compounds
• Screen 5.7: Net Ionic Equations
• Screen 5.11: Gas Forming Reactions
• Screen 5.13: Oxidation Numbers
• Screen 5.15: Solution Concentrations
• Screen 5.16: Preparing Solutions of
Known Concentrations
• Screen 5.17: The pH Scale
• Screen 5.19: Titration

• 5.2: Classifying Solutions by Their Ability
to Conduct Electricity
• 5.3: Guidelines to Predict the Solubility of
Ionic Compounds
• 5.8: An Acid–Base Reaction, HCl and
NaOH
• 5.14: The Reaction of Copper with Nitric
Acid
• 5.18: Making a Solution
• 5.20: pH Values of Some Common
Substances
• 5.23: Titration of an Acid in Aqueous

Solution with a Base

• Screen 5.2: Solutions
• Screen 5.3: Compounds in Aqueous
Solution
• Screen 5.4: Solubility of Ionic
Compounds
• Screen 5.5: Types of Aqueous Solutions
• Screen 5.8: Acids
• Screen 5.9: Bases
• Screen 5.11: Gas Forming Reactions

6
Principles of
Reactivity: Energy
and Chemical
Reactions

• Screen 6.3: Forms of
Energy
• Screen 6.7: Heat
Capacity of Pure
Substances
• Screen 6.10: Calculating
Heat Transfer
• Screen 6.15: Hess’s Law
• Screen 6.17: ProductFavored Systems

• Screen 6.5: Energy Units
• Screen 6.10: Calculating Heat Transfer

• Screen 6.13: Enthalpy Changes for
Chemical Reactions
• Screen 6.14: Measuring Heats of
Reactions
• Screen 6.16: Standard Enthalpy of
Formation

• 6.3: Energy and its Conversion
• 6.8: Exothermic and Endothermic
Processes
• 6.10: Heat Transfer
• 6.11: Heat Transfer and the Temperature
Change for Water
• 6.12: Changes of State
• 6.13: Energy Changes in a Physical
Process
• 6.15: The Exothermic Combustion of
Hydrogen in Air
• 6.17: Constant Volume Calorimeter
• 6.18: Energy Level Diagrams

• Screen 6.4: Directionality of Heat Transfer
• Screen 6.7: Heat Capacity of Pure
Substances
• Screen 6.10: Calculating Heat Transfer
• Screen 6.11: The First Law of
Thermodynamics
• Screen 6.14: Measuring Heats of
Reactions
• Screen 6.15: Hess’s Law

7
Atomic Structure

• Screen 7.5: Planck’s
Equation
• Screen 7.6: Atomic Line
Spectrum
• Screen 7.13: Shapes of
Atomic Orbitals

• Screen 7.3: Electromagnetic Radiation
• Screen 7.6: Atomic Line Spectrum
• Screen 7.8: Wave Properties of the
Electron
• Screen 7.12: Quantum Numbers and
Orbitals

• 7.1: Electromagnetic Radiation
• 7.3: The Electromagnetic Spectrum
• 7.8: The Line Emission Spectrum of
Hydrogen
• 7.10: H Atom in the Bohr Model
• 7.11: Absorption of Energy
• 7.12: Electronic Transitions That Can
Occur in an Excited H Atom
• 7.13: Magnesium Oxide
• 7.14: Different Views of a 1s (n = 1 and
ᐉ = 0) Orbital
• 7.15: Atomic Orbitals

•
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Screen 7.4: Electromagnetic Spectrum
Screen 7.5: Planck’s Equation
Screen 7.6: Atomic Line Spectrum
Screen 7.9: Heisenberg’s Uncertainty
Principle


iii

Media Integration Guide

Chapter

Exercises

Tutorials

Active Figures

Additional Resources

8
Atomic Electron
Configurations

and Chemical
Periodicity

• Screen 8.6: Effective
Nuclear Charge, Z*

• Screen 8.7: Atomic Electron
Configurations
• Screen 8.8: Electron Configuration in
Ions

• 8.2: Observing and Measuring
Paramagnetism
• 8.4: Experimentally Determined Order of
Subshell Energies
• 8.7: Electron Configurations and the
Periodic Table
• 8.9: Examples of the Periodicity of Group
1A and Group 7A Elements
• 8.11: Atomic Radii in Picometers for
Main Group Elements
• 8.13: First Ionization Energies of the
Main Group Elements of the First Four
Periods
• 8.14: Electron Affinity
• 8.15: Relative Sizes of Some Common
Ions

• Screen 8.3: Spinning Electrons and
Magnetism

• Screen 8.6: Effective Nuclear Charge, Z*
• Screen 8.7: Atomic Electron
Configurations
• Screen 8.8: Electron Configuration in Ions
• Screen 8.9: Atomic Properties and
Periodic Trends
• Screen 8.10: Atomic Sizes
• Screen 8.11: Ionization Energy
• Screen 8.12: Electron Affinity
• Screen 8.14: Ion Size
• Screen 8.15: Chemical Reactions and
Periodic Properties

9
Bonding and
Molecular
Structure:
Fundamental
Concepts

• Screen 9.8: Drawing
Lewis Structures
• Screen 9.14:
Determining Molecular
Shape

•
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•
•

•

• 9.3: Lattice Energy
• 9.8: Various Geometries Predicted by
VSEPR
• 9.14: Electronegativity Values for the
Elements According to Pauling
• 9.16: Polarity of Triatomic Molecules,
AB2
• 9.17: Polar and Nonpolar Molecules of
the Type AB3

• Screen 9.2: Valence Electrons
• Screen 9.4: Lattice Energy
• Screen 9.5: Chemical Reactions and
Periodic Properties
• Screen 9.6: Chemical Bond Formation—
Covalent Bonding
• Screen 9.13: Ideal Electron Repulsion
Shapes
• Screen 9.16: Formal Charge
• Screen 9.17: Bond Polarity and
Electronegativity
• Screen 9.18: Molecular Polarity
• Screen 9.19: Bond Properties
• Screen 9.20: Bond Energy and ᭝Hrxn

10
Bonding and
Molecular

Structure: Orbital
Hybridization and
Molecular
Orbitals

• Screen 10.8: Molecular
Fluxionality
• Screen 10.9: Molecular
Orbital Theory
• Screen 10.11:
Homonuclear Diatomic
Molecules

• 10.1: Potential Energy Change During
• Screen 10.5: Sigma Bonding
H¬H Bond Formation
• Screen 10.6: Determining Hybrid Orbitals
• Screen 10.7: Multiple Bonding
• 10.5: Hybrid Orbitals for Two to Six
Electron Pairs
• 10.6: Bonding in the Methane (CH4)
Molecule
• 10.10: The Valence Bond Model of
Bonding in Ethylene, C2H4
• 10.13: Rotation Around Bonds
• 10.22: Molecular Orbital Energy Level
Diagram

Screen 9.7: Lewis Electron Dot Structures
Screen 9.8: Drawing Lewis Structures

Screen 9.9: Resonance Structures
Screen 9.10: Exceptions to the Octet Rule
Screen 9.13: Ideal Electron Repulsion
Shapes
• Screen 9.14: Determining Molecular
Shape

• Screen 10.3: Valence Bond Theory
• Screen 10.4: Hybrid Orbitals
• Screen 10.10: Molecular Orbital
Configurations


Chapter

Exercises

Tutorials

Active Figures

Additional Resources
• Screen 11.3: Hydrocarbons
• Screen 11.4: Hydrocarbons and Addition
Reactions
• Screen 11.6: Functional Groups
• Screens 11.9, 11.10: Synthetic Organic
Polymers

• Screen 11.6: Functional

Groups (1): Reactions of
Alcohols

• Screen 11.4: Hydrocarbons and Addition
Reactions
• Screen 11.6: Functional Groups

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•

12
Gases & Their
Properties

• Screen 12.5: Gas Density
• Screen 12.12: Application of
the Kinetic-Molecular
Theory: Diffusion

• Screen 12.6: Using Gas Laws:
Determining Molar Mass
• Screen 12.7: Gas Laws and Chemical
Reactions: Stoichiometry
• Screen 12.8: Gas Mixtures and Partial
Pressures

• 12.4: An Experiment to Demonstrate

Boyle’s Law
• 12.6: Charles’s Law
• 12.18: Gaseous Diffusion

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•

13
• Screen 13.5: Intermolecular
Intermolecular
Forces (3)
Forces,
• Screen 13.17: Phase Changes
Liquids, and
Solids

• Screen 13.5: Intermolecular Forces (3)
• Screen 13.9: Properties of Liquids

• 13.2: Ion–Dipole Interactions
• 13.8: The Boiling Points of Some Simple
Hydrogen Compounds
• 13.11: The Temperature Dependence of
the Densities of Ice and Water
• 13.17: Vapor Pressure
• 13.18: Vapor Pressure Curves for Diethyl
Ether [(C2H5)2O], Ethanol (C2H5OH),
and Water

• 13.39: Phase Diagram for Water

• Screen 13.2: Phases of Matter
• Screens 13.3, 13.4, 13.5: Intermolecular
Forces
• Screen 13.6: Hydrogen Bonding
• Screen 13.7: The Weird Properties of
Water
• Screens 13.8, 13.9, 13.10, 13.11: Properties
of Liquids
• Screens 13.12, 13.13, 13.14, 13.15: Solid
Structures
• Screens 13.17: Phase Changes

14
• Screen 14.2: Solubility
• Screens 14.5, 14.6: Factors Affecting
Solutions and • Screen 14.5: Factors
Solubility
Their Behavior
Affecting Solubility (1)—
• Screens 14.7, 14.8, 14.9: Colligative
Henry’s Law and Gas Pressure
Properties
• Screens 14.7, 14.8:
Colligative Properties

• 14.6: Solubility of Nonpolar Iodine in
Polar Water and Nonpolar Carbon
Tetrachloride

• 14.9: Dissolving an Ionic Solid in Water

• Screen 14.3: The Solution Process:
Intermolecular Forces
• Screen 14.4: Energetics of Solution
Formation—Dissolving Ionic
Compounds
• Screen 14.9: Colligative Properties

15
Principles of
Reactivity:
Chemical
Kinetics

• 15.2: A Plot of Reactant Concentration
Versus Time for the Decomposition of
N2O5
• 15.7: The Decomposition of H2O2
• 15.9: Half-Life of a First-Order Reaction
• 15.13: Activation Energy
• 15.14: Arrhenius Plot

11.2: Optical Isomers
11.4: Alkanes
11.7: Bacon Fat and Addition Reactions
11.13: Polyethylene
11.18: Nylon-6,6

iv

Media Integration Guide

11
Carbon: More
Than Just
Another
Element

• Screen: 15.4 Concentration
Dependence
• Screen: 15.5 Determination
of the Rate Equation (1)
• Screen 15.12: Reaction
Mechanisms
• Screen 15.13: Reaction
Mechanisms and Rate
Equations
• Screen 15.14: Catalysis and
Reaction Rate

• Screen 15.4: Concentration Dependence
• Screen 15.5: Determination of the Rate
Equation (1)
• Screen 15.6: Concentration–Time
Relationships
• Screen 15.7: Determination of Rate
Equation (2)
• Screen 15.8: Half-Life
• Screen 15.10: Control of Reaction Rates

(3)

Screen 12.3: Gas Laws
Screen 12.4: The Ideal Gas Law
Screen 12.5: Gas Density
Screen 12.9: The Kinetic-Molecular
Theory of Gases: Gases on the Molecular
Scale
• Screen 12.10: Gas Laws and KineticMolecular Theory
• Screen 12.11: Distribution of Molecular
Speeds: Maxwell-Boltzmann Curves
• Screen 12.12: Application of the KineticMolecular Theory: Diffusion

• Screen 15.2: Rates of Chemical Reactions
• Screens 15.3, 15.4, 15.10: Control of
Reaction Rates
• Screen 15.4: Concentration Dependence
• Screen 15.5: Determination of the Rate
Equation (1)
• Screens 15.9, 15.10: Microscopic View of
Reactions
• Screen 15.14: Catalysis and Reaction Rate


Chapter

Exercises

Active Figures

Additional Resources

•
•
•
•

Screen 16.6: Writing Equilibrium Expressions
Screen 16.8: Determining an Equilibrium Constant
Screen 16.9: Systems at Equilibrium
Screen 16.10: Estimating Equilibrium
Concentrations
• Screens 16.12, 16.13: Disturbing a Chemical
Equilibrium

• 16.3: The Reaction of H2
and I2 Reaches
Equilibrium
• 16.9: Changing
Concentrations

•
•
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•
•

Screen 16.2: The Principle of Microscopic Reversibility

Screen 16.3: Equilibrium State
Screen 16.4: Equilibrium Constant
Screen 16.5: The Meaning of the Equilibrium Constant
Screen 16.6: Writing Equilibrium Expressions
Screen 16.9: Systems at Equilibrium
Screens 16.11, 16.13, 16.14: Disturbing a Chemical
Equilibrium

•
•
•
•
•

Screen 17.2: BrØnsted Acids and Bases
Screen 17.4: The pH Scale
Screen 17.5: Strong Acids and Bases
Screen 17.8: Determining K a and Kb Values
Screen 17.9: Estimating the pH of Weak Acid
Solutions
• Screen 17.11: Estimating the pH Following an
Acid-Base Reaction
• Screen 17.13: Lewis Acids and Bases
• Screen 17.15: Neutral Lewis Acids

• 17.2: pH and pOH

•
•
•

•
•
•
•

Screen 17.3: The Acid–Base Properties of Water
Screen 17.4: The pH Scale
Screen 17.6: Weak Acids and Bases
Screen 17.7: Acid–Base Reactions
Screen 17.12: Acid–Base Properties of Salts
Screen 17.14: Cationic Lewis Acids
Screen 17.16: Molecular Interpretation of Acid–Base
Behavior

18
Principles of
Reactivity:
Other Aspects
of Aqueous
Equilibria

•
•
•
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•
•
•

•
•
•

Screen 18.3: Buffer Solutions
Screen 18.4: pH of Buffer Solutions
Screen 18.5: Preparing Buffer Solutions
Screen 18.6: Adding Reagents to a Buffer Solution
Screen 18.7: Titration Curves
Screen 18.12: Solubility Product Constant
Screen 18.13: Determining Ksp, Experimentally
Screen 18.14: Estimating Salt Solubility: Using Ksp
Screen 18.15: Common Ion Effect
Screen 18.16: Solubility and pH
Screen 18.17: Can a Precipitation Reaction Occur?
Screen 18.19: Complex Ion Formation and
Solubility

• 18.2: Buffer Solutions
• 18.5: The Change in pH
During the Titration of a
Weak Acid with a Strong
Base

•
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•

•
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Screen 18.2: Common Ion Effect
Screen 18.3: Buffer Solutions
Screen 18.4: pH of Buffer Solutions
Screen 18.5: Preparing Buffer Solutions
Screen 18.7: Titration Curves
Screen 18.8: Titration of a Weak Polyprotic Acid
Screen 18.9: Titration of a Weak Base with a Strong Acid
Screen 18.10: Acid-Base Indicators
Screen 18.11: Precipitation Reactions
Screen 18.12: Solubility Product Constant
Screen 18.15: Common Ion Effect
Screen 18.16: Solubility and pH
Screen 18.17: Can a Precipitation Reaction Occur?
Screen 18.18: Simultaneous Equilibria
Screen 18.20: Using Solubility

19
Principles of
Reactivity:
Entropy and

Free Energy

• Screen 19.5: Calculating ᭝S for a Chemical
Reaction
• Screen 19.6: The Second Law of Thermodynamics
• Screen 19.7: Gibbs Free Energy
• Screen 19.8: Free Energy and Temperature
• Screen 19.9: Thermodynamics and the Equilibrium
Constant

• 19.12: Spontaneity ᭝G º
with Temperature
• 19.13: Free Energy
Changes as a Reaction
Approaches Equilibrium

•
•
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•
•
•

Screen 19.2: Reaction Spontaneity
Screen 19.3: Directionality of Reactions
Screen 19.4: Entropy: Matter Dispersal and Disorder
Screen 19.6: The Second Law of Thermodynamics
Screen 19.8: Free Energy and Temperature
Screen 19.9: Thermodynamics and the Equilibrium
Constant

16
Principles of
Reactivity:
Chemical
Equilibria

17
Principles of
Reactivity: The
Chemistry of
Acids and
Bases

v

Media Integration Guide

Tutorials

• Screen 17.2:
BrØnsted Acids
and Bases


Chapter

Exercises

Tutorials

• Screen 20.6: Standard Potentials
• Screen 20.8: Cells at Nonstandard
Conditions
• Screen 20.12: Coulometry: Counting
Electrons

20
Principles of
Reactivity:
Electron
Transfer
Reactions

Media Integration Guide

vi

21
The Chemistry
of the Main
Group
Elements

• Screen 21.4: Boron Hydrides
Structures
• Screen 21.5: Aluminum
Compounds
• Screen 21.6: Silicon-Oxygen
Compounds: Formulas and
Structures

• Screen 21.8: Sulfur
Allotropes
• Screen 21.9: Structures of
Sulfur Compounds

22
The Chemistry
of the
Transition
Elements

• Screen 22.2: Formulas and
Oxidation Numbers in
Transition Metal Complexes
• Screen 22.5: Geometry of
Coordination Compounds
• Screen 22.6: Geometric
Isomerism in Coordination
Compounds

23
Nuclear
Chemistry

• Screen 23.5: Kinetics of
Nuclear Decay

• Screen 21.2: Formation of Ionic
Compounds by Main Group Elements

Active Figures
• 20.13: A Voltaic Cell Using Zn 0 Zn (aq,
1.0 M) and H2 0H+(aq, 1.0 M) Half-Cells

• Screen 20.2: Redox Reactions: Electron
Transfer
• Screen 20.3: Balancing Equations for
Redox Reactions
• Screen 20.4: Electrochemical Cells
• Screen 20.5: Batteries
• Screen 20.5: Electrochemical Cells and
Potentials
• Screen 20.6: Standard Potentials
• Screen 20.11: Electrolysis: Chemical
Change from Electrical Energy

• 21.15: Industrial Production of
Aluminum
• 21.22: Compounds and Oxidation
Numbers for Nitrogen
• 21.32: A Membrane Cell for the
Production of NaOH and Cl2 Gas from a
Saturated, Aqueous Solution of NaCl
(Brine)

• 22.8: A Blast Furnace

• Screen 23.2: Radioactive Decay
• Screen 23.3: Balancing Nuclear Reaction
Equations

• Screen 23.4: Stability of Atomic Nuclei
• Screen 23.5: Kinetics of Nuclear Decay

Additional Resources
2+

• Screen 21.7: Electronic Structure in
Transition Metal Complexes
• Screen 21.8: Spectroscopy of Transition
Metal Complexes
• Screen 22.3: Periodic Trends for
Transition Elements

• Screen 23.4: Stability of Atomic Nuclei
• Screen 23.6: Nuclear Fission


Chemistry
& CHEMICAL REACTIVITY
SIXTH EDITION

John C. Kotz
SUNY Distinguished Teaching Professor
State University of New York
College at Oneonta

Paul M. Treichel
Professor of Chemistry
University of Wisconsin–Madison

Gabriela C. Weaver
Associate Professor of Chemistry
Purdue University

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Library of Congress Control Number: 2004109955
Student Edition: ISBN 0-534-99766-X
Volume 1: ISBN 0-495-01013-8

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About the Cover
What lies beneath the Earth’s surface? The mantle of the Earth
consists largely of silicon-oxygen based minerals. But about 2900 km
below the surface the solid silicate rock of the mantle gives way to
the liquid iron alloy core of the planet. To explore the nature of the
rocks at the core-mantle boundary, scientists in Japan examined
magnesium silicate (MgSiO3) at a high pressure (125 gigapascals)
and high temperature (2500 K). The cover image is what they saw.
The solid consists of SiO6 octahedra (blue) and magnesium ions
(Mg2+; yellow spheres). Each SiO6 octahedron shares the four O
atoms in opposite edges with two neighboring octahedra, thus forming a chain of octahedra. These chains are interlinked by sharing the
O atoms at the “top” and “bottom” of SiO6 octahedra in neighboring
chains. The magnesium ions lie between the layers of interlinked
SiO6 chains. For more information see M. Murakami, K. Hirose,
K. Kawamura, N. Sata, and Y. Ohishi, Science, Volume 304, page 855,
May 7, 2004.


ix

Chapter 1

Matter and Measurement

ix

Preface

Brief Contents

Part 1

18 Principles of Reactivity: Other Aspects of Aqueous
Equilibria 848

The Basic Tools of Chemistry
1 Matter and Measurement 10

19 Principles of Reactivity: Entropy and Free Energy

2 Atoms and Elements

20 Principles of Reactivity: Electron Transfer Reactions

58

INTERCHAPTER: The Chemistry of the Environment

3 Molecules, Ions, and Their Compounds

96

4 Chemical Equations and Stoichiometry

140

5 Reactions in Aqueous Solution

902
942

998

Part 5

174

The Chemistry of the Elements

6 Principles of Reactivity: Energy and Chemical
Reactions 232

21 The Chemistry of the Main Group Elements

INTERCHAPTER: The Chemistry of Fuels and Energy
Sources 282

22 The Chemistry of the Transition Elements

Part 2

Appendices

23 Nuclear Chemistry

The Structure of Atoms and Molecules

1012
1068

1108

A

Using Logarithms and the Quadratic Equation A-2

294

B

Some Important Physical Concepts A-7

8 Atomic Electron Configurations and Chemical
Periodicity 332

C

Abbreviations and Useful Conversion Factors A-10

D

Physical Constants A-14

E

Naming Organic Compounds A-16

10 Bonding and Molecular Structure: Orbital Hybridization
and Molecular Orbitals 436

F

Values for the Ionization Energies and Electron Affinities
of the Elements A-19

11 Carbon: More than Just Another Element

G

Vapor Pressure of Water at Various Temperatures A-20

H

Ionization Constants for Weak Acids at 25 °C A-21

I

Ionization Constants for Weak Bases at 25 °C A-23

J

Solubility Product Constants for Some Inorganic
Compounds at 25 °C A-24

K

Formation Constants for Some Complex Ions in Aqueous
Solution A-26

L

Selected Thermodynamic Values A-27

M

Standard Reduction Potentials in Aqueous Solution
at 25 °C A-33

N

Answers to Exercises A-36

O

Answers to Selected Study Questions A-56

P

Answers to Selected Interchapter Study Questions A-107

7 Atomic Structure

9 Bonding and Molecular Structure: Fundamental
Concepts 372

474

INTERCHAPTER: The Chemistry of Life: Biochemistry

530

Part 3

States of Matter
12 Gases and Their Properties

546

13 Intermolecular Forces, Liquids, and Solids

588

INTERCHAPTER: The Chemistry of Modern Materials
14 Solutions and Their Behavior 656

642

Part 4

The Control of Chemical Reactions
15 Principles of Reactivity: Chemical Kinetics
16 Principles of Reactivity: Chemical Equilibria
17 Principles of Reactivity: Chemistry of Acids
and Bases 796

698
756

ix

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xi

Chapter 1

Matter and Measurement

xi

Preface

Contents
This text is available in these student versions:
• Complete text ISBN 0-534-99766-X • Volume 1 (Chapters 1–12) ISBN 0-495-01013-8
• Volume 2 (Chapters 12–23) ISBN 0-495-01014-6 • Two-volume set ISBN 0-534-40800-1

Preface

1.8

xxiii

A Preface to Students

Mathematics of Chemistry

Exponential or Scientific Notation

2

Significant Figures
Graphing

The Basic Tools of Chemistry
Matter and Measurement
How Hot Is It?

Key Equations

10

Study Questions

Classifying Matter 12
States of Matter and Kinetic-Molecular Theory 13
Matter at the Macroscopic and Particulate Levels 14
Pure Substances 14
Mixtures: Homogeneous and Heterogeneous 15
Elements and Atoms

1.3

Compounds and Molecules

1.4

Physical Properties 20

Density 20
Temperature Dependence of Physical Properties
Extensive and Intensive Properties 23

2

1.6

Units of Measurement 25
Temperature Scales 26
Length 28
Volume 30
Chemical Perspectives: It’s a Nanoworld!
Mass 32

58

58

2.2

Atomic Number and Atomic Mass 67
Atomic Number 67
Relative Atomic Mass and the Atomic Mass Unit
Mass Number 67

22

23

31
2.3

Charles D. Winters

48

Protons, Electrons, and Neutrons: Development of
Atomic Structure 60
Electricity 60
Radioactivity 60
Cathode-Ray Tubes and the Characterization
of Electrons 61
Protons 64
Neutrons 64
Historical Perspectives: Uncovering Atomic Structure 65
The Nucleus of the Atom 65

Making Measurements: Precision, Accuracy, and
Experimental Error 32
A Closer Look: Standard Deviation 33

page 19

46

2.1

18

Physical and Chemical Changes

44

47

Atoms and Elements
Stardust

17

1.5

41

43

Chapter Goals Revisited

10

1.2

1.7

38

Problem Solving and Chemical Arithmetic

Charles D. Winters

1.1

35

Problem Solving by Dimensional Analysis

Part 1

1

35

Isotopes 69
Isotope Abundance 69
Determining Atomic Mass and Isotope
Abundance 70
A Closer Look: Atomic Mass and the Mass Defect

2.4

Atomic Weight

2.5

Atoms and the Mole 73
Historical Perspectives: Amedeo Avogadro
and His Number 74
Molar Mass 74

67

71

72

page 25

xi


xii

Contents

3.4

Molecular Compounds: Formulas, Names,
and Properties 114

3.5

Formulas, Compounds, and the Mole

3.6

Describing Compound Formulas 119
Percent Composition 119
Empirical and Molecular Formulas from Percent
Composition 121

A Closer Look: Mass Spectrometry, Molar Mass,
and Isotopes 127

3.7

Hydrated Compounds

Charles D. Winters

Chapter Goals Revisited
Key Equations

116

128
130

131

Study Questions

132

page 82

2.6

2.7

2.8

4

The Periodic Table 77
Features of the Periodic Table 77
Developing the Periodic Table 80
Historical Perspectives: Periodic Table 81

Black Smokers and the Origin of Life

An Overview of the Elements, Their Chemistry, and the
Periodic Table 82
Group 1A, Alkali Metals: Li, Na, K, Rb, Cs, Fr 82
Group 2A, Alkaline Earth Metals: Be, Mg, Ca,
Sr, Ba, Ra 82
Group 3A: B, Al, Ga, In, Tl 82
Group 4A: C, Si, Ge, Sn, Pb 83
Group 5A: N, P, As, Sb, Bi 85
Group 6A: O, S, Se, Te, Po 85
Group 7A, Halogens: F, Cl, Br, I, At 86
Group 8A, Noble Gases: He, Ne, Ar, Kr, Xe, Rn 86
The Transition Elements 87
Essential Elements
Key Equations
Study Questions

Chemical Equations 142
Historical Perspectives: Antoine Laurent Lavoisier
(1743–1794) 143

4.2

Balancing Chemical Equations

4.3

Mass Relationships in Chemical Reactions:
Stoichiometry 148

4.4

Reactions in Which One Reactant Is Present
in Limited Supply 152
A Stoichiometry Calculation with a Limiting
Reactant 153

4.5

Percent Yield

4.6

Chemical Equations and Chemical Analysis
Quantitative Analysis of a Mixture 158
Determining the Formula of a Compound
by Combustion 162

89

Key Equation

90

Molecules, Ions, and Their Compounds
DNA: The Most Important Molecule

3.1

Molecules, Compounds, and Formulas
Formulas 99

96

Molecular Models 100
A Closer Look: Computer Resources for Molecular
Modeling 102

3.3

Ionic Compounds: Formulas, Names,
and Properties 103
Ions 104
Formulas of Ionic Compounds 107
Names of Ions 109
Names of Ionic Compounds 111
Properties of Ionic Compounds 111

165

166

96
5

Reactions in Aqueous Solution
Salt

98

3.2

158

165

Study Questions

3

145

157

Chapter Goals Revisited

89

140

140

4.1

88

Chapter Goals Revisited

Chemical Equations and Stoichiometry

174

174

5.1

Properties of Compounds in Aqueous Solution
Ions in Aqueous Solution: Electrolytes 176
Types of Electrolytes 177
Solubility of Ionic Compounds in Water 179

5.2

Precipitation Reactions 181
Net Ionic Equations 183

5.3

Acids and Bases 185
Acids 185
Chemical Perspectives: Sulfuric Acid 187

A Closer Look: The H + Ion in Water 188

176


xiii

Contents

Bases 188
Oxides of Nonmetals and Metals 189
Chemical Perspectives: Limelight and Metal Oxides

190

5.4

Reactions of Acids and Bases

5.5

Gas-Forming Reactions

5.6

Classifying Reactions in Aqueous Solution 195
A Summary of Common Reaction Types
in Aqueous Solution 196
A Closer Look: Product-Favored and Reactant-Favored
Reactions 197

5.7

5.8

Temperature and Heat 237
Systems and Surroundings 238
Directionality of Heat Transfer: Thermal
Equilibrium 238
A Closer Look: Why Doesn’t the Heat in a Room Cause Your
Cup of Coffee to Boil? 239
Energy Units 240
Chemical Perspectives: Food and Calories 241

191

194

Oxidation–Reduction Reactions 197
Redox Reactions and Electron Transfer 198
Oxidation Numbers 200
A Closer Look: Are Oxidation Numbers “Real”? 201
Recognizing Oxidation–Reduction Reactions 202
Measuring Concentrations of Compounds
in Solution 205
Solution Concentration: Molarity 205
Preparing Solutions of Known Concentration

209

5.9

pH, a Concentration Scale for Acids and Bases

5.10

Stoichiometry of Reactions in Aqueous Solution
General Solution Stoichiometry 214
Titration: A Method of Chemical Analysis 216
Chapter Goals Revisited
Key Equations
Study Questions

212

6.2

Specific Heat Capacity and Heat Transfer 241
A Closer Look: Sign Conventions 243
Quantitative Aspects of Heat Transfer 244

6.3

Energy and Changes of State

6.4

The First Law of Thermodynamics 250
Historical Perspectives: Work, Heat, Cannons, Soup,
and Beer 251

A Closer Look: P-V Work 252
Enthalpy 253
State Functions 254

6.5

Enthalpy Changes for Chemical Reactions

6.6

Calorimetry 257
Constant Pressure Calorimetry: Measuring ΔH 257
Constant Volume Calorimetry: Measuring ΔE 259

6.7

Hess’s Law 261
Energy Level Diagrams

214

221

223
223

Principles of Reactivity: Energy and Chemical
Reactions 232
Energy: Some Basic Principles
Conservation of Energy 236

Study Questions

236

270

271
272

INTERCHAPTER
The Chemistry of Fuels and Energy
Sources 282
Supply and Demand: The Balance Sheet on Energy
Energy Consumption 283
Energy Resources 284
Fossil Fuels 284
Coal 285
Natural Gas 286
Petroleum 286
Other Fossil Fuel Sources
Charles D. Winters

6.1

Key Equations

232

268

Product- or Reactant-Favored Reactions and
Thermochemistry 269
Chapter Goals Revisited

page 145

Charles D. Winters

Abba’s Refrigerator

254

262

6.8 Standard Enthalpies of Formation 265
Enthalpy Change for a Reaction 267
A Closer Look: Hess’s Law and Equation 6.6
6.9

6

246

page 214

287

Energy in the Future: Choices and Alternatives
Fuel Cells 288

A Hydrogen Economy 289
Biosources of Energy 291
Solar Energy 292

288

283


xiv

Contents

What Does the Future Hold for Energy?
Suggested Readings
Study Questions

8

292

292

293

Everything in Its Place
8.1

Part 2

The Structure of Atoms
and Molecules
7

Atomic Structure
Colors in the Sky

7.1

7.2

7.3

294

Electromagnetic Radiation 296
Wave Properties 296
Standing Waves 298
The Visible Spectrum of Light 299

Atomic Line Spectra and Niels Bohr 305
Atomic Line Spectra 305
The Bohr Model of the Hydrogen Atom 307
The Bohr Theory and the Spectra
of Excited Atoms 309
A Closer Look: Experimental Evidence for Bohr’s Theory

304

Quantum Mechanical View of the Atom 314

Historical Perspectives: 20th-Century Giants
of Science 315
The Uncertainty Principle 315
Schrödinger’s Model of the Hydrogen Atom and Wave
Functions 316
Quantum Numbers 316
Useful Information from Quantum Numbers 318
320

Atomic Orbitals and Chemistry

323

Chapter Goals Revisited
Key Equations
Study Questions

8.3

Atomic Subshell Energies and Electron
Assignments 339
Order of Subshell Energies and Assignments
Effective Nuclear Charge, Z* 341

325
326

324

Atomic Electron Configurations 343

Electron Configurations of the Main Group
Elements 343
Electron Configurations of the Transition
Elements 349

8.5

Electron Configurations of Ions

8.6

Atomic Properties and Periodic Trends
Atomic Size 353
Ionization Energy 357
Electron Affinity 359
Ion Sizes 361

8.7

Periodic Trends and Chemical Properties
Study Questions

353

363

365

366

Bonding and Molecular Structure:
Fundamental Concepts 372
Molecules in Space

9.1

372

Valence Electrons 374
Lewis Symbols for Atoms

339

351

313

9

336
337

338

8.4

313

7.5

7.7

The Pauli Exclusion Principle

Chapter Goals Revisited

The Wave Properties of the Electron

The Shapes of Atomic Orbitals
s Orbitals 320
p Orbitals 321
d Orbitals 323
f Orbitals 323

Electron Spin 334
Magnetism 334
Paramagnetism and Unpaired Electrons 335
A Closer Look: Paramagnetism and Ferromagnetism

8.2

294

Planck, Einstein, Energy, and Photons 300
Planck’s Equation 300
Einstein and the Photoelectric Effect 302
Energy and Chemistry: Using Planck’s Equation
Chemical Perspectives: UV Radiation, Skin Damage,
and Sunscreens 305

332

Chemical Perspectives: Quantized Spins and MRI

7.4

7.6

Atomic Electron Configurations and
Chemical Periodicity 332

375

9.2

Chemical Bond Formation

376

9.3

Bonding in Ionic Compounds 377
Ion Attraction and Lattice Energy 378
Why Don’t Compounds Such as NaCl2 and
NaNe Exist? 381

9.4

Covalent Bonding and Lewis Structures
Lewis Electron Dot Structures 382

The Octet Rule 383
Predicting Lewis Structures 386

382


xv

Contents

9.5

9.6

Resonance 390
A Closer Look: Resonance Structures, Lewis Structures, and
Molecular Models 391

Key Equations
Study Questions

Exceptions to the Octet Rule 392
Compounds in Which an Atom Has Fewer Than Eight
Valence Electrons 393
Compounds in Which an Atom Has More Than Eight
Valence Electrons 393
Chemical Perspectives: The Importance of Odd-Electron
Molecules 396

9.7

Molecular Shapes 397
Central Atoms Surrounded Only
by Single-Bond Pairs 398
Central Atoms with Single-Bond Pairs
and Lone Pairs 399
Central Atoms with More Than Four Valence Electron
Pairs 401
Multiple Bonds and Molecular Geometry 403

9.8

Charge Distribution in Covalent Bonds
and Molecules 405
Formal Charges on Atoms 405
A Closer Look: Formal Charge and Oxidation
Number 407
Bond Polarity and Electronegativity 408
A Closer Look: Electronegativity 410
Combining Formal Charge and Bond Polarity

Molecular Polarity 413
Historical Perspectives: Developing Concepts of Bonding
and Structure 415
Chemical Perspectives: Cooking with Microwaves 416

9.10

Bond Properties: Order, Length, and Energy
Bond Order 419

Bond Length 419
Bond Energy 421
The DNA Story—Revisited

10

427

Bonding and Molecular Structure: Orbital
Hybridization and Molecular Orbitals 436
Orbitals and Bonding Theories

10.2

Valence Bond Theory 439
Orbital Overlap Model of Bonding 439
Hybridization of Atomic Orbitals 441
Multiple Bonds 450
Cis-Trans Isomerism: A Consequence of p
Bonding 454
Benzene: A Special Case of p Bonding 455

10.3

Molecular Orbital Theory 457
Principles of Molecular Orbital Theory 457
Bond Order 459
Molecular Orbitals of Li2 and Be2 460
Molecular Orbitals from Atomic p Orbitals 461
Electron Configurations for Homonuclear Molecules for

Boron Through Fluorine 462
A Closer Look: Molecular Orbitals for Compounds Formed from
p-Block Elements 464
Electron Configurations for Heteronuclear Diatomic
Molecules 465
Resonance and MO Theory 465
Chapter Goals Revisited

419

Key Equations
Study Questions

424

11
J. Hester and P. Scowan, of Arizona State University, and NASA.

Scott Camazine & Sue Trainor/Photo Researchers, Inc.

page 373

436

10.1

438

467

467
468

Carbon: More Than Just Another Element
A Colorful Beginning

page 339

425

427

Linus Pauling: A Life of Chemical Thought

411

9.9

9.11

Chapter Goals Revisited

474

11.1

Why Carbon? 476
Structural Diversity 476
Isomers 477
A Closer Look: Writing Formulas and Drawing

Structures 478
A Closer Look: Optical Isomers and Chirality 480
Stability of Carbon Compounds 480

11.2

Hydrocarbons 481
Alkanes 481
A Closer Look: Flexible Molecules 487
Alkenes and Alkynes 487
Aromatic Compounds 492
A Closer Look: Petroleum Chemistry 495

474


xvi

Alcohols, Ethers, and Amines 496
Alcohols and Ethers 497
Properties of Alcohols and Ethers 499
Amines 500

11.4

Compounds with a Carbonyl Group 502
Aldehydes and Ketones 503
Carboxylic Acids 504
A Closer Look: Glucose and Sugars 506
Chemical Perspectives: Aspirin Is More Than

100 Years Old! 507
Esters 507
Amides 509
A Closer Look: Fats and Oils 510

11.5

Polymers 512
Classifying Polymers 512
Addition Polymers 513
Condensation Polymers 517
Chemical Perspectives: Super Diapers
Chapter Goals Revisited
Study Questions

520

Nucleic Acids 537
Nucleic Acid Structure 537
Protein Synthesis 538
The RNA World and the Origin of Life

The Ideal Gas Law 557
The Density of Gases 559
Calculating the Molar Mass of a Gas from P, V, and T
Data 560

12.4

Gas Laws and Chemical Reactions

12.5

Gas Mixtures and Partial Pressures 564
Historical Perspectives: Studies on Gases 567

12.6

The Kinetic-Molecular Theory of Gases 567
Molecular Speed and Kinetic Energy 567
Kinetic-Molecular Theory and the Gas Laws 570

12.7

Diffusion and Effusion

12.8

Some Applications of the Gas Laws
and Kinetic-Molecular Theory 573
Separating Isotopes 573
Deep Sea Diving 574

Concluding Remarks
Suggested Readings

544

12.9

Nonideal Behavior: Real Gases 575
Chemical Perspectives: The Earth’s Atmosphere

531

542

544

544

Chapter Goals Revisited
Key Equations
Study Questions

Part 3

States of Matter
12

Gases and Their Properties

550

12.3

540

Metabolism 541
Energy and ATP 541

Chemical Perspectives: AIDS and Reverse Transcriptase
Oxidation–Reduction and NADH 543
Respiration and Photosynthesis 543

The Properties of Gases 548
Gas Pressure 548
A Closer Look: Measuring Gas Pressure

Gas Laws: The Experimental Basis 550
The Compressibility of Gases: Boyle’s Law 550
The Effect of Temperature on Gas Volume:
Charles’s Law 552
Combining Boyle’s and Charles’s Laws:
The General Gas Law 554
Avogadro’s Hypothesis 556

522

530

page 568

12.2

520

Proteins 531
Amino Acids Are the Building Blocks of Proteins
Protein Structure and Hemoglobin 533
Sickle Cell Anemia 533

Enzymes, Active Sites, and Lysozyme 535

Study Questions

page 515

12.1

INTERCHAPTER
The Chemistry of Life: Biochemistry

Charles D. Winters

11.3

Christopher Springmann/Corbisstockmarket.com

Contents

13
546

561

571

577

578

579
580

Intermolecular Forces, Liquids,
and Solids 588
The Mystery of the Disappearing Fingerprints

Up, Up, and Away!

546

13.1

588

States of Matter and the Kinetic-Molecular Theory

590


xvii

Intermolecular Forces 591
Interactions Between Ions and Molecules with a
Permanent Dipole 592
Interactions Between Molecules with
Permanent Dipoles 594
A Closer Look: Hydrated Salts 595
Interactions Involving Nonpolar Molecules 596

13.3

Hydrogen Bonding 599
Hydrogen Bonding and the Unusual Properties
of Water 602

13.4

Summary of Intermolecular Forces

13.5

Properties of Liquids 606
Vaporization 606
Vapor Pressure 609
Boiling Point 613
Critical Temperature and Pressure 613
Surface Tension, Capillary Action, and Viscosity

13.6

13.7
13.8

13.9

Charles D. Winters

13.2

Charles D. Winters

Contents

604

page 646

Fired Ceramics for Special Purposes: Cements, Clays,
and Refractories 651
Modern Ceramics with Exceptional Properties 652

614

The Solid State: Metals 616
Crystal Lattices and Unit Cells 617
A Closer Look: Packing Oranges 621

Biomaterials: Learning from Nature
The Future of Materials
Suggested Readings

The Solid State: Structures and Formulas
of Ionic Solids 622
Other Kinds of Solid Materials
Molecular Solids 625
Network Solids 625
Amorphous Solids 626

Study Questions

14

Key Equation

633

634

INTERCHAPTER
The Chemistry of Modern Materials

The Solution Process 662
Liquids Dissolving in Liquids 662
A Closer Look: Supersaturated Solutions
Solids Dissolving in Water 664
Heat of Solution 666

659

663

14.3

Factors Affecting Solubility: Pressure
and Temperature 669
Dissolving Gases in Liquids: Henry’s Law

14.4

Colligative Properties 672
Changes in Vapor Pressure: Raoult’s Law 672
Boiling Point Elevation 674
Freezing Point Depression 677
Colligative Properties and Molar Mass
Determination 678
Colligative Properties of Solutions
Containing Ions 679
Osmosis 681
A Closer Look: Reverse Osmosis in Tampa Bay 685

14.5

Colloids 686
Types of Colloids 687
Surfactants 688

644

Chapter Goals Revisited
Key Equations

650

656

656

Units of Concentration

642

Semiconductors 645
Bonding in Semiconductors: The Band Gap 646
Applications of Semiconductors: Diodes, LEDs,
and Transistors 647
Microfabrication Techniques Using
Semiconductor Materials 648
Ceramics 649
Glass: A Disordered Ceramic

Solutions and Their Behavior

14.2

631

Metals 643
Bonding in Metals 643
Alloys: Mixtures of Metals

655

14.1

634

Study Questions

654

655

The Killer Lakes of Cameroon

630

Chapter Goals Revisited

653

625

The Physical Properties of Solids 627
Melting: Conversion of Solid to Liquid 627
Sublimation: Conversion of Solid to Vapor 628

13.10 Phase Diagrams
Water 630
Carbon Dioxide

page 651

Study Questions

691
692

690

669


xviii

Contents

Part 4

The Control
of Chemical Reactions

Faster and Faster

698

15.1

Rates of Chemical Reactions

15.2

Reaction Conditions and Rate

15.3

Effect of Concentration on Reaction Rate
Rate Equations 707
The Order of a Reaction 707
The Rate Constant, k 709

Determining a Rate Equation 709

15.4

15.5

15.6

700
704
page 686

706

Concentration—Time Relationships: Integrated
Rate Laws 712
First-Order Reactions 713
Second-Order Reactions 715
Zero-Order Reactions 716
Graphical Methods for Determining Reaction Order
and the Rate Constant 716
Half-Life and First-Order Reactions 719
A Microscopic View of Reaction Rates 722
Concentration, Reaction Rate, and Collision
Theory 722
Temperature, Reaction Rate, and Activation
Energy 723
A Closer Look: Reaction Coordinate Diagrams 726
Effect of Molecular Orientation on Reaction Rate
The Arrhenius Equation 727

Effect of Catalysts on Reaction Rate 729
A Closer Look: Enzymes: Nature’s Catalysts 732

726

Key Equations

16.3

Determining an Equilibrium Constant

16.4

Using Equilibrium Constants in Calculations 772
Calculations Where the Solution Involves a Quadratic
Expression 774

16.5

More About Balanced Equations and Equilibrium
Constants 777

16.6

Disturbing a Chemical Equilibrium 781
Effect of Temperature Changes on Equilibrium
Composition 781
Effect of the Addition or Removal of a Reactant
or Product 783
Effect of Volume Changes on Gas-Phase Equilibria

16.7

Applying the Principles of Chemical Equilibrium
The Haber-Bosch Process 787
Key Equations
Study Questions

17

741

770

788

789
789

796

17.1

Acids, Bases, and the Equilibrium Concept

744

17.2

The Brønsted-Lowry Concept of Acids and Bases

Conjugate Acid–Base Pairs 802

16

Principles of Reactivity: Chemical
Equilibria 756

17.3

16.1

The Nature of the Equilibrium State

Water and the pH Scale 802
Water Autoionization and the Water Ionization
Constant, K w 803
The pH Scale 805
Determining and Calculating pH 806

16.2

The Equilibrium Constant and Reaction Quotient
Writing Equilibrium Constant Expressions 763

17.4

Equilibrium Constants for Acids and Bases
Aqueous Solutions of Salts 810

Study Questions

Fertilizer and Poison Gas

756
758
760

785
787

Principles of Reactivity: The Chemistry
of Acids and Bases 796
Nature’s Acids

743

page 763

A Closer Look: Equilibrium Constant Expressions for Gases–Kc
and Kp 764
The Meaning of the Equilibrium Constant, K 765
The Reaction Quotient, Q 767

Chapter Goals Revisited

Reaction Mechanisms 732
Molecularity of Elementary Steps 733
Rate Equations for Elementary Steps 734
Molecularity and Reaction Order 734
Reaction Mechanisms and Rate Equations 736

Chapter Goals Revisited

Charles D. Winters

Principles of Reactivity: Chemical
Kinetics 698
Charles D. Winters

15

798

806

799


xix

Contents

A Logarithmic Scale of Relative Acid Strength, pK a 812
Relating the Ionization Constants for an Acid and Its
Conjugate Base 813
17.5

Equilibrium Constants and Acid–Base Reactions
Predicting the Direction of Acid–Base Reactions

17.6

Types of Acid–Base Reactions 816
The Reaction of a Strong Acid with a Strong Base 816
The Reaction of a Weak Acid with a Strong Base 817
The Reaction of Strong Acid with a Weak Base 817
The Reaction of a Weak Acid with a Weak Base 818

18

Principles of Reactivity: Other Aspects
of Aqueous Equilibria 848
Roses Are Red, Violets Are Blue, and Hydrangeas Are
Red or Blue 848

814
814
18.1

The Common Ion Effect

850

18.2

Controlling pH: Buffer Solutions 854
General Expressions for Buffer Solutions
Preparing Buffer Solutions 857
How Does a Buffer Maintain pH? 860

856

17.7

Calculations with Equilibrium Constants 818
Determining K from Initial Concentrations and
Measured pH 818
What Is the pH of an Aqueous Solution of a Weak Acid
or Base? 820
What Is the pH of a Solution After an Acid–Base
Reaction? 824

18.3

Acid–Base Titrations 861
Current Perspectives: Buffers in Biochemistry 862
Titration of a Strong Acid with a Strong Base 862
Titration of a Weak Acid with a Strong Base 864
Titration of Weak Polyprotic Acids 867
Titration of a Weak Base with a Strong Acid 868
pH Indicators 870

17.8

Polyprotic Acids and Bases

18.4

17.9

The Lewis Concept of Acids and Bases

Cationic Lewis Acids 829
Molecular Lewis Acids 830

Solubility of Salts 873
The Solubility Product Constant, K sp 873
Relating Solubility and K sp 875
A Closer Look: Solubility Calculations 877
Solubility and the Common Ion Effect 879
The Effect of Basic Anions on Salt Solubility 882

18.5

Precipitation Reactions 884
K sp and the Reaction Quotient, Q 884
K sp, the Reaction Quotient, and Precipitation
Reactions 885

18.6

Solubility and Complex Ions

18.7

Solubility, Ion Separations, and Qualitative
Analysis 890

826
828

17.10 Molecular Structure, Bonding, and Acid–Base

Behavior 832
Why Is HF a Weak Acid Whereas HCl Is
a Strong Acid? 832
Chemical Perspectives: Lewis and Brønsted Bases: Adrenaline
and Serotonin 833
Why Is HNO2 a Weak Acid Whereas HNO3 Is a Strong
Acid? 833
Why Are Carboxylic Acids Brønsted Acids? 835
Why Are Hydrated Metal Cations Brønsted Acids? 836
Why Are Anions Brønsted Bases? 836
Why Are Organic Amines Brønsted
and Lewis Bases? 836
Chapter Goals Revisited

Study Questions

838

19

839

892

893
894

Principles of Reactivity: Entropy
and Free Energy 902
Perpetual Motion Machines

page 882

page 921

902

19.1

Spontaneous Change and Equilibrium

19.2

Heat and Spontaneity

19.3

Dispersal of Energy and Matter 906
Dispersal of Energy 906
Dispersal of Matter 907
Applications of the Dispersal of Matter 909
The Boltzmann Equation for Entropy 911
A Summary: Matter and Energy Dispersal 911

19.4

Entropy and the Second Law of Thermodynamics 912
A Closer Look: Reversible and Irreversible Processes 914
Entropy Changes in Physical and Chemical
Processes 915

Charles D. Winters

Study Questions

Key Equations

837

Charles D. Winters

Key Equations

Chapter Goals Revisited

887

904

904


xx
19.5

19.6

19.7

19.8

Contents

Entropy Changes and Spontaneity 917
Calculating ¢S°sys, the Entropy Change
for the System 918
Calculating ¢S°surr, the Entropy Change for the
Surroundings 918
Calculating ¢S°univ, the Total Entropy Change for the
System and Surroundings 918
In Summary: Spontaneous or Not? 919
Gibbs Free Energy 921
ΔG° and Spontaneity 922
What Is “Free” Energy? 922
Calculating ΔG°rxn, the Free Energy Change
for a Reaction 923
Standard Free Energy of Formation 924
Free Energy and Temperature 925

Electrochemistry and Thermodynamics 978
Work and Free Energy 978
E° and the Equilibrium Constant 979
Historical Perspectives: Electrochemistry and Michael
Faraday 981

20.7

Electrolysis: Chemical Change Using Electrical
Energy 981
Electrolysis of Molten Salts 982

Electrolysis of Aqueous Solutions 983

20.8

Counting Electrons
Key Equations
Study Questions

989

990
990

INTERCHAPTER
The Chemistry of the Environment 998
Water, Water, Everywhere 999
Removing Suspended Particles from Water
Hard Water 1001
Filtration 1003
Disinfection of Water 1003

933

934

942

20.1

Oxidation–Reduction Reactions 945

Balancing Oxidation–Reduction Equations

20.2

Simple Voltaic Cells 952
Voltaic Cells with Inert Electrodes 955
Electrochemical Cell Conventions 956
Chemical Perspectives: Frogs and Voltaic Piles

946

Green Chemistry 1007
DDT: Dichlorodiphenyltrichloroethane 1007
CFCs: Chlorofluorocarbons 1008
Regulating Pollutants 1010
Reducing Pollutants through Green Chemistry

957

Commercial Voltaic Cells 957
Primary Batteries: Dry Cells and Alkaline
Batteries 958
Secondary or Rechargeable Batteries 959
Fuel Cells 960
Chemical Perspectives: Your Next Car? 962
Standard Electrochemical Potentials 962
Electromotive Force 963
Measuring Standard Potentials 963
A Closer Look: EMF, Cell Potential, and Voltage 965
Standard Reduction Potentials 965

Tables of Standard Reduction Potentials 967
Using Tables of Standard Reduction Potentials 969
Chemical Perspectives: An Electrochemical
Toothache! 973

1000

Air: Now You See It, Now You Don’t 1004
Composition of the Atmosphere 1004
Particulates 1004
The PM Index 1005
Particulates and Visibility 1005
Particulate Air Pollution 1006

Principles of Reactivity: Electron
Transfer Reactions 942
Blood Gases

986

930

934

Study Questions

20.4

20.6

Thermodynamics, Time, and Life 931
Chemical Perspectives: Thermodynamics and Speculation on
the Origin of Life 932
Key Equations

20.3

Electrochemical Cells Under Nonstandard
Conditions 974
The Nernst Equation 975

Chapter Goals Revisited

ΔG°, K, and Product Favorablility 928
Free Energy, the Reaction Quotient, and the
Equilibrium Constant 929
Using the Relationship Between ΔG°rxn and K

Chapter Goals Revisited

20

20.5

For More Information
Study Questions

1010

1011

1011

Part 5

The Chemistry of the Elements
21

The Chemistry of the Main Group
Elements 1012
Sulfur Chemistry and Life on the Edge

21.1

Element Abundances

1014

1012


xxi

Contents

Silicates with Sheet Structures
and Aluminosilicates 1041
Silicone Polymers 1042
Chemical Perspectives: Lead Pollution,
Old and New 1043

21.2

21.3

21.4

21.5

21.6

21.7

page 1052

The Periodic Table: A Guide to the Elements 1015
Valence Electrons 1015
Ionic Compounds of Main Group Elements 1015
Molecular Compounds of Main Group Elements 1017
Hydrogen 1019
Chemical and Physical Properties of Hydrogen 1019
A Closer Look: Hydrogen, Helium, and Balloons 1020
Preparation of Hydrogen 1021
The Alkali Metals, Group 1A 1022
Preparation of Sodium and Potassium 1023
Properties of Sodium and Potassium 1024
A Closer Look: The Reducing Ability
of the Alkali Metals 1025
Important Lithium, Sodium, and Potassium
Compounds 1025

The Alkaline Earth Elements, Group 2A 1027
Properties of Calcium and Magnesium 1028
Metallurgy of Magnesium 1028
Calcium Minerals and Their Applications 1029
Chemical Perspectives: Alkaline Earth Metals
and Biology 1030
Chemical Perspectives: Of Romans, Limestone, and
Champagne 1031
Boron, Aluminum, and the Group 3A Elements 1032
The General Chemistry of the Group 3A
Elements 1032
Boron Minerals and Production of the Element 1032
Metallic Aluminum and Its Production 1033
Boron Compounds 1034
Aluminum Compounds 1037
Silicon and the Group 4A Elements 1038
Silicon 1038
Silicon Dioxide 1039
Silicate Minerals with Chain and Ribbon
Structures 1040

Nitrogen, Phosphorus, and the Group 5A
Elements 1043
Properties of Nitrogen and Phosphorus 1044
A Closer Look: Making Phosphorus 1045
Nitrogen Compounds 1045
Hydrogen Compounds of Phosphorus and Other Group
5A Elements 1048
Phosphorus Oxides and Sulfides 1048
Phosphorus Oxoacids and Their Salts 1050

21.9

Oxygen, Sulfur, and the Group 6A Elements 1052
Preparation and Properties of the Elements 1052
Sulfur Compounds 1054

© Ludovic Maisant/Corbis

Arthur N. Palmer
page 1013

21.8

21.10 The Halogens, Group 7A 1055
Preparation of the Elements 1055
Fluorine Compounds 1058
Chlorine Compounds 1059
Chapter Goals Revisited
Study Questions

22

1061

1061

The Chemistry of the Transition
Elements 1068
Memory Metal

1068

22.1

Properties of the Transition Elements 1070
Electron Configurations 1072
Oxidation and Reduction 1072
Chemical Perspectives: Corrosion of Iron 1074
Periodic Trends in the d-Block: Size, Density, Melting
Point 1075

22.2

Metallurgy 1076
Pyrometallurgy: Iron Production 1077
Hydrometallurgy: Copper Production 1079

22.3

Coordination Compounds 1080
Complexes and Ligands 1080
Formulas of Coordination Compounds 1083
A Closer Look: Hemoglobin 1084
Naming Coordination Compounds 1086

22.4

Structures of Coordination Compounds 1087
Common Coordination Geometries 1087

Isomerism 1088

22.5

Bonding in Coordination Compounds 1092
The d Orbitals: Ligand Field Theory 1092
Electron Configurations and Magnetic Properties

1094


xxii
22.6

Contents

Colors of Coordination Compounds 1097
Color 1097
The Spectrochemical Series 1098
A Closer Look: A Spectrophotometer 1100

Analytical Methods: Isotope Dilution 1137
Space Science: Neutron Activation Analysis and the
Moon Rocks 1138
Food Science: Food Irradiation 1138

Chapter Goals Revisited

Chapter Goals Revisited

Study Questions

1102

Key Equations

1103

1140

Study Questions

23

Nuclear Chemistry
Nuclear Medicine

Appendices

1108

Natural Radioactivity

23.2

Nuclear Reactions and Radioactive Decay
Equations for Nuclear Reactions 1111
Radioactive Decay Series 1113
Other Types of Radioactive Decay 1115

23.4

1110
1111

Stability of Atomic Nuclei 1116
The Band of Stability and Radioactive Decay
Nuclear Binding Energy 1119

1117

Rates of Nuclear Decay 1122
Half-Life 1122
Kinetics of Nuclear Decay 1123
Radiocarbon Dating 1125

23.5

Artificial Nuclear Reactions 1127
A Closer Look: The Search for New Elements

23.6

Nuclear Fission

1130

23.7

Nuclear Fusion

1132

23.8

Radiation Health and Safety 1132
Units for Measuring Radiation 1132
Radiation: Doses and Effects 1133
A Closer Look: What Is a Safe Exposure? 1134

23.9

1141

1108

23.1

23.3

1139

1129

Applications of Nuclear Chemistry 1135
Nuclear Medicine: Medical Imaging 1135
Nuclear Medicine: Radiation Therapy 1136
Analytical Methods: The Use of Radioactive Isotopes
as Tracers 1136
A Closer Look: Technetium-99m 1137

A-1

A

Using Logarithms and the Quadratic Equation

A-2

B

Some Important Physical Concepts

C

Abbreviations and Useful Conversion Factors

D

Physical Constants

E

Naming Organic Compounds

F

Values for the Ionization Energies and Electron
Affinities of the Elements A-19

G

Vapor Pressure of Water at Various Temperatures

H

Ionization Constants for Weak Acids at 25 °C

A-21
A-23

A-7
A-10

A-14
A-16

I

Ionization Constants for Weak Bases at 25 °C

J

Solubility Product Constants for Some Inorganic
Compounds at 25 °C A-24

K

Formation Constants for Some Complex Ions in
Aqueous Solution A-26

L

Selected Thermodynamic Values

M

Standard Reduction Potentials in Aqueous Solution
at 25 °C A-33

N

Answers to Exercises

O

Answers to Selected Study Questions

P

Answers to Selected Interchapter Study
Questions A-107

Glossary/Index

I-1

A-27

A-36

A-56

A-20


xxiii

Chapter 1

Matter and Measurement

xxiii

Preface

Preface
e are gratified that Chemistry & Chemical Reactivity has been used by more than
a million students in its first five editions. Because this is one indication our
book has been successful in helping students learn chemistry, we believe the goals
we set out in the first edition are still appropriate. Our principal goals have always
been to provide a broad overview of the principles of chemistry, the reactivity of the
chemical elements and their compounds, and the applications of chemistry. We
have organized this approach around the close relation between the observations
chemists make of chemical and physical changes in the laboratory and in nature
and the way these changes are viewed at the atomic and molecular levels.
Another of our goals has been to convey a sense of chemistry not only as a
field that has a lively history but also as one that is highly dynamic, with important
new developments occurring every year. Furthermore, we want to provide some insight into the chemical aspects of the world around us. Indeed, a major objective
of this book is to provide the tools needed for you to function as a chemically literate citizen. Learning something of the chemical world is just as important as understanding some basic mathematics and biology, and as important as having an
appreciation for history, music, and literature. For example, you should know

which materials are important to our economy, what some of the reactions in
plants and animals and in our environment are, and what role chemists play in
protecting the environment.
Among the most exciting and satisfying aspects of our careers as chemists has
been our ability to discover new compounds and to find new ways to apply chemical
principles and explain what we observe. We hope we have conveyed that sense of enjoyment in this book as well as our awe at what is known about chemistry—and, just
as important, what is not known!

Charles D. Winters

W

page 36

Emerging Developments
in Content Usage and Delivery
The use of media, presentation tools, and homework management tools has expanded significantly in the last three years. About ten years ago we incorporated
electronic media into this text with the first edition of our interactive CD-ROM. It
has been used by thousands of students worldwide and has been the most successful
attempt to date to encourage students to interact with chemistry.
Multimedia technology has evolved over the past ten years, and so have our
students. Students are not only focused on conceptual understanding, but are also
keenly aware of the necessity of preparing for examinations. Our challenge as authors and educators is to use students’ focus on assessment as a way to help them
reach a higher level of conceptual understanding. In light of this goal, we have
made major changes in our integrated media program. We have found that few
students explore multimedia for its own sake. Therefore, we have redesigned the
media so that students now have the opportunity to interact with media based on
xxiii

xxiv

Preface

clearly stated chapter goals that are correlated to end-of-chapter questions. By using new diagnostic tools, students will be directed to specific resources based on
their levels of understanding. This new program, called General ChemistryNow, is described in detail later. The closely related OWL homework management system has
also been used by tens of thousands of students, and we are pleased to announce
that selected end-of-chapter questions are now available for use within the OWL
system.

Charles D. Winters

Audience for the Textbook, the General
ChemistryNow CD-ROM and Website, and OWL

page 52

The textbook, CD-ROM and website, and OWL are designed to serve introductory
courses in chemistry for students interested in further study in science, whether that
science is biology, chemistry, engineering, geology, physics, or related subjects. Our
assumption is that students beginning this course have had some preparation in algebra and in general science. Although undeniably helpful, a previous exposure to
chemistry is neither assumed nor required.

Philosophy and Approach of the Program
We have had three major, albeit not independent, goals since the first edition of the
book. The first goal was to write a book that students would enjoy reading and that
would offer, at a reasonable level of rigor, chemistry and chemical principles in a
format and organization typical of college and university courses today. Second, we
wanted to convey the utility and importance of chemistry by introducing the properties of the elements, their compounds, and their reactions as early as possible and
by focusing the discussion as much as possible on these subjects. Finally, with the

new, integrated media program, we hope to bring students to a higher level of conceptual understanding.
The American Chemical Society has been urging educators to put “chemistry”
back into introductory chemistry courses. We agree with this position wholeheartedly. Therefore, we have tried to describe the elements, their compounds, and their
reactions as early and as often as possible in several ways. First, numerous color photographs depict reactions occurring, the elements and common compounds, and
common laboratory operations and industrial processes. Second, we have tried to
bring material on the properties of elements and compounds as early as possible
into the Exercises and Study Questions and to introduce new principles using realistic chemical situations. Finally, relevant highlights are given in Chapters 21 and 22
as a capstone to the principles described earlier.

Organization of the Book
Chemistry & Chemical Reactivity has two overarching themes: chemical reactivity and
bonding and molecular structure. The chapters on principles of reactivity introduce the
factors that lead chemical reactions to be successful in converting reactants to products. Under this topic you will study common types of reactions, the energy involved in reactions, and the factors that affect the speed of a reaction. One reason
for the enormous advances in chemistry and molecular biology in the last several
decades has been an understanding of molecular structure. Sections of the book
on principles of bonding and molecular structure lay the groundwork for understanding
these developments. Particular attention is paid to an understanding of the structural aspects of such biologically important molecules as DNA.