Understanding Essential Chemistry

Max Diem, PhD, FSAS, was based in the Department of Chemistry and Chemical Biology at Northeastern University in Boston. He did his first degree at the University of Karlsruhe and then his PhD at the University of Toledo in OH. From 1978 to 2005, he rose through the ranks from Assistant Professor to Professor of Chemistry at the City University of New York (Hunter College) before moving to Northeastern University. His research interests are centered on the development of physical / optical methods for medical diagnosis in tissue diagnostics.

• Preface xiAbout the Companion Website xiii1 The Metric System and Mathematical Tools 11.1 Scientific Notation and Significant Figures 11.2 The Metric System 21.3 Manipulations of Exponential Expressions 41.4 Equations, Proportionality, and Graphs 51.5 Quadratic, Cubic, and Quartic Equations 71.6 Exponential Functions and Logarithms 81.7 Radial and Spherical Polar Coordinates 111.8 Differential and Integral Calculus 121.9 Differential Equations 141.10 Complex Numbers 152 Atoms, Elements, and the Periodic System 172.1 Subatomic Particles and Atoms 172.2 Elements, Isotopes, and Ions 182.3 The Periodic Chart and Periodic Properties of the Elements 212.4 Definition of Atomic Masses, Avogadro’s Number, and the Mole 26Further Reading 283 Molecules, Compounds, Bonding, and Percent Composition 293.1 Ionic Compounds 293.2 Molecules with Covalent Bonds 303.3 Molecules with Polar Covalent Bonds and Lewis Structures 313.4 Molecular Compounds and the (Gram) Molecular Mass 373.5 Percent Composition and Empirical Formulae 38Further Reading 394 Chemical Reactions 414.1 Chemical Reaction and Stoichiometry 414.2 Limiting Reagents, Theoretical Yield, and Percent Yield 424.3 Solutions: General Aspects 434.4 Solution Stoichiometry: Molarity, Molality, Mole Fraction, Dilutions 454.5 Precipitation Reactions 47Further Reading 495 Electronic Structure of Atoms 515.1 Description of Light as an Electromagnetic Wave 515.2 Particle Properties of Light and Wave-particle Duality 525.3 The Hydrogen Atom Emission Spectrum: Stationary Atomic States 555.4 Hydrogen Atom Orbitals 585.5 Atoms with Multiple Electrons: The Aufbau Principle Revisited 62Further Reading 676 Chemical Bonding: Covalent Bonding, Molecular Geometries, and Polarity 696.1 General Aspects of Covalent Bonding 696.2 Lewis and VB Theory 696.3 Hybridization and Multiple Bonding 706.4 VSEPR Model 736.5 Molecular Polarity 756.6 MO Theory 76Further Reading 817 Solids and Liquids: Bonding and Characteristics 837.1 Metals and Semiconductors 837.2 Ionic Solids 857.3 Covalent Solids 867.4 Intermolecular Forces 877.4.1 Hydrogen Bonding 877.4.2 Dipole–Dipole Interactions 887.4.3 London Dispersion Forces (Induced Dipole Forces) 897.5 Macromolecular Solids 897.6 Liquids and Solutions 907.6.1 General Aspects of Solutions and Solvation 907.6.2 Colligative Properties 90Further Reading 938 The Gaseous State 958.1 General Properties of Gases 958.2 Empirical Gas Laws 978.3 The Ideal Gas Law 998.4 Real Gases 1008.5 Gaseous Mixtures and Partial Pressures 1018.6 Kinetic Theory of Gases 1028.7 Diffusion and Effusion of Gases 104Further Reading 1069 Chemical Equilibrium 1079.1 What Is a System “at Equilibrium”? 1079.2 Liquid–Vapor Phase Equilibrium: Vapor Pressure 1089.3 Temperature Dependence of Vapor Pressure 1109.4 Chemical Equilibrium and the Equilibrium Constant 1139.5 Equilibrium Calculations 1159.6 Direction of a Chemical Reaction and the Concentration Quotient Q 1199.7 Numerical Determination of Equilibrium Constants from Experimental Data 1209.8 Perturbations of Equilibria: Le Chatelier’s Principle 1209.9 Solubility and Solubility Product 1229.9.1 The Solubility Product Constant, Ksp 1239.9.2 Solubility Calculations 1239.9.3 Common Ion Effect 1249.9.4 Experimental Determination of Ksp 1259.9.5 Precipitation Reactions 126Further Reading 12710 Acids and Bases 12910.1 What Are Acids/Bases? 12910.2 Strong Acids and Bases; Definition of pH and pOH 13010.3 Weak Acids/Bases 13110.4 The Relationship Between pH and pOH: Self-dissociation of Water 13410.5 Common Ion Effect 13510.6 Acidic and Basic Salts 13610.7 Buffers 13810.8 Acid–Base Titrations 14010.8.1 Titration of a Strong Acid with a Strong Base 14110.8.2 Titration of a Weak Acid with a Strong Base 14310.8.3 Acid–Base Indicators 145Further Reading 14611 Thermodynamics: Energy, Energy Conversions, and Spontaneity 14711.1 Energetics of Chemical Reactions 14711.2 Thermochemistry 14711.2.1 Definition of Energy, Work, and Heat 14711.2.2 Calorimetry: Measurement of Heat Flow 15011.3 The First Law of Thermodynamics 15211.4 State Functions 15311.5 Definition of Enthalpy 15311.6 Hess’ Law and Reaction Enthalpies 15411.6.1 Enthalpy of Crystal Formation: Lattice Energy of MgO 15611.7 Enthalpy of Phase Transitions 15711.8 Entropy 15811.8.1 Entropy and Probability 16111.8.2 Entropy and Heat Flow 16211.8.3 Entropy as an Indicator of Energy Exhaustion 16311.9 Free Enthalpy 16411.10 Free Enthalpy and Equilibrium 165Further Reading 16812 Reduction–Oxidation (Redox) Reactions and Electrochemistry 16912.1 Oxidation State and Oxidation Numbers: Balancing Redox Equations 17012.2 Galvanic Cells, Electric Work, and Electromotive Force 17312.3 Batteries 17712.3.1 Alkaline Dry Cell (AA Battery) 17712.3.2 Lead–Acid Battery 17812.3.3 Lithium-ion Battery 18012.4 Relationship Between Cell Potential and Free Enthalpy 18112.5 Concentration and Temperature Dependence of EMF 181Further Reading 18313 Chemical Kinetics: Rates of Reactions and Reaction Mechanisms 18513.1 Scope of Kinetics Discussion 18513.2 Elementary Steps and Chemical Reactions 18513.2.1 Kinetic Model of Chemical Reactions 18513.2.2 Basics of Chemical Kinetics: Rate Law and Rate Constant 18713.2.3 Time Dependence of the Reaction Rate 18813.2.4 Integrated Rate Law 18913.3 Rates of Multistep Reactions, and Equilibria 19113.4 Reaction Rates for Reactions That Are Nonlinear in Concentrations 19413.5 Reaction Path and Catalysis 195Further Reading 19814 Nuclear Reactions 19914.1 Nuclear Reactions and Transmutations 19914.2 The Structure of Atomic Nuclei 19914.3 Radioactive Decay and Decay Chains 20014.3.1 α-Decay 20014.3.2 β-Decay 20014.3.3 γ-Emission (γ-Decay) 20114.3.4 Positron Emission 20214.3.5 Nuclear Decay Chains 20214.3.6 Nuclear Dating 20314.4 Nuclear Fission and Nuclear Fusion 20414.4.1 Nuclear Binding Energy 20514.4.2 Nuclear Fusion 20514.4.3 Nuclear Fission 206Further Reading 20715 Fundamentals of Quantum Chemistry, Spectroscopy, and Structural Chemistry 20915.1 Wavefunctions and the 1D and 2D Particle in a Box 20915.2 Spherical Harmonics, Hydrogen Atom Wavefunctions, and Hydrogen Atomic Orbitals 21315.3 Atomic Energy Levels and Atomic Emission Spectroscopy 21715.4 Molecular Energy Levels, Spectroscopy, and Structural Methods 21915.4.1 Electronic Energy Levels and UV-vis Absorption Spectroscopy 21915.4.2 Vibrational Energy Levels and Infrared Spectroscopy 22115.4.3 Rotational Energy Levels and Microwave Spectroscopy 22515.4.4 Nuclear Magnetic Resonance Spectroscopy 22615.4.5 X-ray Diffraction 22815.5 Mass Spectrometry 230Further Reading 230Epilogue 231Appendix 233List of Constants 233List of Abbreviations and Symbols 234Index 235