Chemistry: Structure and Dynamics

CONTENTS

Chapter 1 Elements and Compounds

1.1 Chemistry: A Definition
1.2 Physical and Chemical Properties
1.3 Elements, Compounds, and Mixtures
1.4 Evidence for the Existence of Atoms
Research in the 90s: Scanning Tunneling Microscopy
1.5 The Structure of Atoms
1.6 Atomic Symbols
1.7 Atomic Number and Mass Number
1.8 Isotopes
1.9 Ions
1.10 Polyatomic Ions
1.11 Predicting the Formulas of ionic Compounds
1.12 The Periodic Table
1.13 Metals, Nonmetals, and Semimetals
Problems

Chapter 2 The Mole: The Link Between The Macroscopic and the Atomic World of Chemistry

2.1 The Macroscopic, Atomic, and Symbolic Worlds of Chemistry
2.2 The Mass of an Atom
2.3 The Mole as the Bridge Between the Macroscopic and Atomic Scales
2.4 The Mole as a Collection of Atoms
2.5 Converting Grams into Moles
2.6 Chemical Formulas
2.7 The Mole as a Collection of Molecules
2.8 Chemical Reactions and the Law of Conservation of Atoms
2.9 Chemical Equations as a Representation of Chemical Reactions
2.10 Two Views of Chemical Equations: Molecules Versus Moles
2.11 Balancing Chemical Equations
2.12 Mole Ratios and Chemical Equations
2.13 Stoichiometry
Research in the 90s: The Stoichiometry of the Breathalyzer
2.14 Determining the Formula of a Compound
2.15 Elemental Analysis
2.16 The Nuts and Bolts of Limiting Reagents
Problems

Chapter 3 The Structure of The Atom

3.1 Rutherford's Model of the Atom
3.2 Particles and Waves
3.3 Light and Other Forms of Electromagnetic Radiation
3.4 Atomic Spectra
3.5 Quantization of Energy
3.6 The Bohr Model of the Atom
3.7 The Energy Levels of the Hydrogen Atom
3.8 The First ionization Energy
3.9 The Shell Model
3.10 The Shell Model and the Periodic Table
3.11 Photoelectron Spectroscopy and the Structure of Atoms
3.12 Electron Configurations from Photoelectron Spectroscopy
3.13 Orbitals and the Pauli Exclusion Principle
3.14 Predicting Electron Configurations
3.15 Electron Configurations and the Periodic Table
3.16 Electron Configurations and Hund's Rules
3.17 Wave Properties of the Electron
3.18 The Size of Atoms: Metallic Radii
3.19 The Size of Atoms: Covalent Radii
3.20 The Relative Size of Atoms and Their Ions
3.21 Patterns in ionic Radii
3.22 Second, Third, Fourth, and Higher ionization Energies
3.23 Average Valence Electron Energy (AVEE)
3.24 AVEE and Metallicity
Problems

Chapter 4 The Covalent Bond

4.1 Valence Electrons
4.2 The Covalent Bond
4.3 How Does the Sharing of Electrons Bond Atoms.
4.4 Using Lewis Structures to Understand the Formation of Bonds
4.5 Drawing Skeleton Structures
4.6 A Step-By-Step Approach to Writing Lewis Structures
4.7 Molecules That Don't Seem to Satisfy the Octet Rule
4.8 Bond Lengths
4.9 Resonance Hybrids
4.10 Electronegativity
4.11 Formal Charge
4.12 Partial Charge
4.13 The Shapes of Molecules
Research in the 90s: The Shapes of Molecules
4.14 Predicting the Shapes of Molecules (Electron Domain Theory)
4.15 The Role of Nonbonding Electrons in the ED Theory
4.16 Bond Angles
4.17 The Difference Between Polar Bonds and Polar Molecules
Problems

Chapter 4 Appendix

Special Topics
A.1 The Shapes of Orbitals
A.2 Hybrid Atomic Orbitals
A.3 Molecules with Double and Triple Bonds
A.4 Molecular Orbital Theory
Problems

Chapter 5 Ionic and Metallic Bonds

5.1 The Active Metals
5.2 Main-Group Metals and their Ions
5.3 Main-Group Nonmetals and their Ions
5.4 Transition-Metals and their Ions
5.5 Predicting the Products of Reactions that Produce ionic Compounds
5.6 Oxides, Peroxides, and Superoxides
5.7 The ionic Bond
5.8 The Structure of ionic Compounds
5.9 Metallic Bonds
5.10 The Relationship Between ionic, Covalent, and Metallic Bonds
5.11 Bond Type Triangles
5.12 Limitations of Bond Type Triangles
5.13 Oxidation Numbers
5.14 Calculating Oxidation Numbers
5.15 Oxidation-Reduction Reactions
5.16 Nomenclature
Problems

Chapter 6 Gases

6.1 Temperature
6.2 Temperature as a Property of Matter
6.3 The States of Matter
6.4 Elements or Compounds That Are Gases at Room Temperature
6.5 The Properties of Gases
6.6 Pressure Versus Force
6.7 Atmospheric Pressure
6.8 Boyle's Law
6.9 Amontons' Law
6.10 Charles' Law
6.11 Gay-Lussac's Law
6.12 Avogadro's Hypothesis
6.13 The Ideal Gas Equation
6.14 Ideal Gas Calculations: Part I
6.15 Ideal Gas Calculations: Part II
6.16 Dalton's Law of Partial Pressures
6.17 The Kinetic Molecular Theory
6.18 How the Kinetic Molecular Theory Explains the Gas Laws
Problems

Chapter 6 Appendix

Special Topics
6A.1 Graham's Laws of Diffusion and Effusion
6A.2 The Kinetic Molecular Theory and Graham's Laws
6A.3 Deviations from Ideal Gas Law Behavior: Van der Waals Equation
6A.4 Analysis of the Van Der Waals Constants
Problems

Chapter 7 Making and Breaking of Bonds

7.1 Energy
7.2 Heat
7.3 Heat and the Kinetic Molecular Theory
7.4 The First Law of Thermodynamics
7.5 State Functions
7.6 The Enthalpy of the System
7.7 Enthalpies of Reaction
7.8 Enthalpy as a State Function
7.9 Standard-State Enthalpies of Reaction
7.10 Enthalpies of Reaction
7.11 Enthalpies of Atom Combination
7.12 Using Enthalpies of Atom Combination to Probe Chemical Reactions
7.13 Bond Length and Enthalpy of Atom Combination
Problems

Chapter 7 Appendix

Special Topics
7A.1 Hess's Law
7A.2 Enthalpies of Formation
Problems

Chapter 8 Liquids and Solutions

8.1 Gases, Liquids, and Solids
8.2 Intermolecular Forces
8.3 The Structure of Liquids
8.4 The Vapor Pressure of a Liquid
8.5 Melting Point and Freezing Point
8.6 Boiling Point
8.7 The Kinetic Theory of Liquids
8.8 Heat Capacity
8.9 Hydrogen Bonding and the Anomalous Properties of Water
8.10 Solute, Solvent and Solution
8.11 Solutions: Like Dissolves Like
8.12 Why Do Some Solids Dissolve in Water
8.13 Solubility Equilibria
8.14 Solubility Rules
8.15 Hydrophilic and Hydrophobic Molecules
8.16 Soaps, Detergents, and Dry-Cleaning Agents
8.17 Solution Concentration
8.18 Molarity as a Way of Counting Atoms in Solution
8.19 Dilution
Problems

Chapter 9 Solids

9.1 Solids
9.2 Molecular and Network Covalent Solids
9.3 Ionic Solids
9.4 Metallic Solids
9.5 Physical Properties That Result From the Structure of Metals
9.6 The Structure of Metals and Other Monatomic Solids
9.7 Coordination Numbers and the Structures of Metals
9.8 Unit Cells: The Simplest Repeating Unit in a Crystal
9.9 Measuring the Distance Between Particles in a Unit Cell
9.10 Determining the Unit Cell of a Crystal
9.11 Calculating the Size of an Atom or Ion
9.12 Semimetals
9.13 The Search for New Materials
Research in the 90s: The Search for High Temperature Superconductors
Problems

Chapter 10 An Introduction to Kinetics and Equilibrium

10.1 Reactions That Don't Go to Completion
10.2 Gas-Phase Reactions
10.3 The Rate of a Chemical Reaction
10.4 The Collision Theory Model of Gas Phase Reactions
10.5 Equilibrium Constant Expressions
10.6 Reaction Quotients: A Way to Decide Whether a Reaction Is at Equilibrium
10.7 Changes in Concentration That Occur as a Reaction Comes to Equilibrium
10.8 Hidden Assumptions That Make Equilibrium Calculations Easier
10.9 The Effect of Temperature on an Equilibrium Constant
10.10 LeChatelier's Principle
10.11 Equilibrium Reactions Which Involve Pure Solids and Liquids
10.12 LeChatelier's Principle and The Haber Process
Problems

Chapter 10 Appendix

Special Topics
10.A1 A Rule of Thumb for Testing the Validity of Assumptions
10.A2 What do We Do When the Approximations Fail?
Problems

Chapter 11 Acids and Bases

11.1 Properties of Acids and Bases
11.2 The Arrhenius Definition of Acids and Bases
11.3 The Bronsted Definition of Acids and Bases
11.4 Conjugate Acid-Base Pairs
11.5 The Role of Water in the Bronsted Theory
11.6 To What Extent Does Water Dissociate to Form Ions?
11.7 pH as a Measure of the Concentration of the H₃O⁺ Ion
11.8 The Relative Strengths of Acids and Bases
11.9 The Relative Strengths of Conjugate Acid-Base Pairs
11.10 The Relative Strengths of Pairs of Acids and Bases
11.11 Relationship of Structure to Relative Strengths of Acids and Bases
11.12 Strong Acid pH Calculations
11.13 Weak Acid pH Calculations
11.14 Base pH Calculations
11.15 Mixtures of Acids and Bases
11.16 Buffers and Buffer Capacity
11.17 Buffer Capacity and pH Titration Curves
Problems

Chapter 11 Appendix

Special Topics
11A.1 Diprotic Acids
11A.2 Diprotic Bases
11A.3 Triprotic Acids
11A.4 Compounds That Could Be Either Acids or Bases
Problems

Chapter 12 Oxidation-Reduction Reactions

12.1 Common Oxidation-Reduction Reactions
12.2 Determining Oxidation Numbers
12.3 Recognizing Oxidation-Reduction Reactions
12.4 Voltaic Cells
12.5 Oxidizing and Reducing Agents
12.6 Relative Strengths of Oxidizing and Reducing Agents
12.7 Standard-State Cell Potentials
12.8 Electrochemical Cells at Nonstandard Conditions
12.9 Batteries
Problems

Chapter 12 Appendix I

Special Topics I
12A.1 Electrolytic Cells
12A.2 The Electrolysis of Molten NaCl
12A.3 The Electrolysis of Aqueous NaCl
12A.4 Electrolysis of Water
12A.5 Faraday's Law
12A.6 Galvanic Corrosion and Cathodic Protection
Problems

Chapter 12 Appendix II

Special Topics II
12AII.I Electrochemical Cells at Nonstandard Conditions: The Nernst Equation
12AII.2 Balancing Oxidation-Reduction Equations
12AII.3 Redox Reactions in Acidic Solutions
12AII.4 Redox Reactions in Basic Solutions
12AII.5 Molecular Redox Reactions
Problems

Chapter 13 Chemical Thermodynamics

13.1 Spontaneous Chemical Reactions
13.2 Entropy as a Measure of Disorder
13.3 Entropy and the Second Law of Thermodynamics
13.4 Standard-State Entropies of Reaction
13.5 The Third Law of Thermodynamics
13.6 Calculating Entropy Changes for Chemical Reactions
13.7 Gibbs Free Energy
13.8 The Effect of Temperature on the Free Energy of a Reaction
13.9 Beware of Oversimplifications
13.10 Standard-State Free Energies of Reaction
13.11 Interpreting Standard-State Free Energy of Reaction Data
13.12 The Relationship Between Free Energy and Equilibrium Constants
13.13 Equilibria Expressed in Partial Pressures
13.14 The Temperature Dependence of Equilibrium Constants
Problems

Chapter 14 Kinetics

14.1 The Forces That Control a Chemical Reaction
14.2 Chemical Kinetics
14.3 Is the Rate of Reaction Constant?
14.4 Instantaneous Rates of Reaction
14.5 Rate Laws and Rate Constants
14.6 A Physical Analog of Kinetic Systems
14.7 The Rate Law Versus the Stoichiometry of a Reaction
14.8 Order and Molecularity
14.9 A Collision Theory Model of Chemical Reactions
14.10 The Mechanisms of Chemical Reactions
14.11 Zero-Order Reactions
14.12 Determining the Order of a Reaction from Rates of Reaction
14.13 The Integrated Form of First-Order and Second-Order Rate Laws
14.14 Determining the Order of a Reaction with the Integrated Form of Rate Laws
14.15 Reactions That Are First Order in Two Reactants
14.16 The Activation Energy of Chemical Reactions
14.17 Catalysts and the Rates of Chemical Reactions
14.18 Determining the Activation Energy of a Reaction
14.19 The Kinetics of Enzyme-Catalyzed Reactions
Problems

Chapter 14 Appendix

Special Topics
14A.1 Deriving the Integrated Rate Laws

Chapter 15 Chemical Analysis

15.1 Methods of Analysis
15.2 Separation of Mixtures
15.3 The Olive Oil Caper
15.4 The Great Apple Scare of '89
15.5 Fighting Crime with Chemistry
15.6 Interaction of Electromagnetic Radiation with Matter--Spectroscopy
15.7 The Fox River Mystery
15.8 An Off Color Fatty Alcohol
15.9 The Search for New Compounds
15.10 The Search for the Northwest Passage-- The Franklin Expedition
15.11 Dead Cats
Problems

A.1 Systems of Units

English Units of Measurement
The Metric System
Sl Units of Measurement
Derived Sl Units
Non-SI Units

A.2 Uncertainty in Measurement

Systematic and Random Errors/Accuracy and Precision
Accuracy and Precision

A.3 Significant Figures

Addition and Subtraction with Significant Figures
Multiplication and Division with Significant Figures
The Difference Between Measurements and Definitions
Rounding off

A.4 Scientific Notation

A.5 The Graphical Treatment of Data A-10

Table B.1 Values of Selected Fundamental Constants
Table B.2 Selected Conversion Factors
Table B.3 The Vapor Pressure of Water
Table B.4 Radii of Atoms and Ions
Table B.5 Ionization Energies
Table B.6 Electron Affinities
Table B.7 Electronegativities
Table B.8 Acid-Dissociation Equilibrium Constants
Table B.9 Base-lonization Constants
Table B.10 Solubility Product Equilibrium Constants
Table B.11 Complex Formation Equilibrium Constants
Table B.12 Standard Reduction Potentials
Table B.13 Bond-Dissociation Enthalpies
Table B.14 Standard-State Enthalpies, Free Energies and Entropies of Atom Combination

Answers to Selected Problems