Fundamentals of Chemistry: A Modern Introduction (1966)

Fundamentals of Chemistry: A Modern Introduction focuses on the formulas, processes, and methodologies used in the study of chemistry. The book first looks at general and historical remarks, definitions of chemical terms, and the classification of matter and states of aggregation. The text then discusses gases. Ideal gases; pressure of a gas confined by a liquid; Avogadro's Law; and Graham's Law are described. The book also discusses aggregated states of matter, atoms and molecules, chemical equations and arithmetic, thermochemistry, and chemical periodicity. The text also highlights the electronic structures of atoms. Quantization of electricity; spectra of elements; quantization of the energy of an electron associated with nucleus; the Rutherford-Bohr nuclear theory; hydrogen atom; and representation of the shapes of atomic orbitals are explained. The text also highlights the types of chemical bonds, hydrocarbons and their derivatives, intermolecular forces, solutions, and chemical equilibrium. The book focuses as well on ionic solutions, galvanic cells, and acids and bases. It also discusses the structure and basicity of hydrides and oxides. The reactivity of hydrides; charge of dispersal and basicity; effect of anionic charge; inductive effect and basicity; and preparation of acids are described. The book is a good source of information for readers wanting to study chemistry.

Preface

1: Introduction

1.1 General and Historical Remarks

1.2 Definitions of Some Chemical Terms

1.3 The Classification of Matter; States of Aggregation

Problems

2: Gases

2.1 Introduction

2.2 Ideal Gases

2.3 The Law of Charles and Gay-Lussac; Absolute Temperature; V ∞ T, or V = Constant X T

2.4 Boyle's Law; V ∞ 1/F , Or Pv = Constant

2.5 Dalton's Law of Partial Pressures; P ∞ Ν; Ρ = Constant X N; PT = P1 + P2 + . . .

2.6 The Pressure of a Gas Confined by a Liquid

2.7 Avogadro's Law; V ∞ N; V = Constant X N

2.8 Graham's Law; U ∞ L/√m; u = Constant/√m

2.9 The Ideal Gas Law; The Mole; Gas Densities; PV = nRT

2.10 Deviations from Ideal Behavior

Problems

Additional Problems

3: Aggregated States of Matter

3.1 Introduction

3.2 Solids; Methods of Investigation

3.3 The Space Lattice; The Unit Cell

3.4 The Tetrahedron; The Octahedron

3.5 Real Crystals; Crystal Habits; Lattice Defects

3.6 Liquids; Glasses

3.7 Viscosity; Fluidity; Surface Tension; Wetting; Capillarity

3.8 Changes of State

3.9 Spontaneous Change; Entropy

3.10 Liquid-Gas Interconversion; Vapor Pressure

3.11 The Vapor Pressure of Water; Humidity

3.12 Critical Constants

3.13 Boiling

3.14 Melting Point; Freezing Point; Warming and Cooling Curves

3.15 The Phase Diagram

3.16 Colloid.; Adsorbents

Problems

Additional Problems

4: Atoms and Molecules

4.1 The Law of Conservation of Matter

4.2 The Law of Definite Proportions

4.3 The Atomic Theory

4.4 The Law of Multiple Proportions

4.5 The Law of Combining Volumes; The Avogadro Hypothesis

4.6 Molecular Weights of Gases

4.7 Atomic Weights from Molecular Weights; The Cannizzaro Method

4.8 Atomic Weights from Specific Heats; The Method of Petit and Dulong

4.9 Molecular Formulas

4.10 Empirical Formulas; Ionic Solids

4.11 More Accurate Atomic Weights

4.12 Mass Spectroscopy

4.13 Inertial and Gravitational Mass

Problems

Additional Problems

5: Chemical Equations and Chemical Arithmetic

5.1 Formulas and Valence

5.2 Nomenclature

5.3 Chemical Equations

5.4 Quantitative Information from Chemical Equations

5.5 Percent Yield

Problems

Additional Problems

6: Thermochemistry; The First Law of Thermodynamics

6.1 Thermochemistry

6.2 Hess's Law

6.3 Bond Dissociation Energy

6.4 The Interconvertibility of Matter and Energy

6.5 The First Law of Thermodynamics

Problems

Additional Problems

7: Chemical Periodicity

7.1 Before Mendeleev

7.2 Mendeleev; Meyer

7.3 The Periodic Law and The Periodic Table

7.4 The Periodicity of Valence

7.5 The Periodicity of Chemical Properties

Problems

8: Electronic Structures of Atoms

8.1 Quantization of Electricity

8.2 The Positive Ions (Positive Rays)

8.3 The Rutherford-Bohr Nuclear Theory of The Atom

8.4 The Nature of Light

8.5 Spectra of Elements

8.6 Quantization of The Energy of an Electron Associated with Nucleus

8.7 Modification of The Bohr Theory

8.8 Matter Waves

Wave (Quantum) Mechanics

8.9 The Wave Equation

8.10 The Oscillating Electron

8.11 The Hydrogen Atom

8.12 Atomic Orbitals; Shells and Subshells

8.13 Energy of an Orbital; Degeneracy; Distribution of Electrons In Atoms

8.14 The Physical Significance of "Psi Square"

8.15 The Sign of a Wave Function

8.16 Representations of The Shapes of Atomic Orbitals

8.17 Electron Revolution and Spin

8.18 Paramagnetism

8.19 Atomic Structure and Periodic Properties of Atoms

Problems

Additional Problems

9: Types of Chemical Bonds

9.1 Lewis Symbols

9.2 Ionic Bond

9.3 Energetics of Formation of Ionic Solids; Born-Haber Cycle

9.4 Ionic Crystals; Radius Ratio Rule

9.5 Covalent Bond

9.6 Multiple Bonds

9.7 Multiple Bonding and Size of Atoms

9.8 Comparison of Properties of Ionic and Covalent Compounds

9.9 Polar Covalent Bonds; Electronegativity

9.10 Exceptions To The Octet Rule

9.11 Coordinate Covalent Bond

9.12 Formal Charge and Oxidation Number

9.13 Writing Lewis Structures

9.14 Periodicity of Chemical Bonding and Oxidation Number

9.15 Epilogue

Problems

Additional Problems

10: Hydrocarbons and Their Derivatives

10.1 Bonding of Carbon

10.2 Alkane Hydrocarbons

10.3 Isomerism

10.4 Nomenclature of Alkanes

10.5 Alkenes and Alkynes; Unsaturated Hydrocarbons

10.6 Addition Reaction of Unsaturated Hydrocarbons

10.7 Cycloalkanes and Cycloalkenes

10.8 Dienes; Benzene and Aromatic Compounds

10.9 Functional Group Derivatives

10.10 Summary

Problems

Additional Problems

11: The Covalent Bond

11.1 Introduction

11.2 Molecular Orbital Method

11.3 Valence Bond Approach

11.4 Hybridization of Atomic Orbitals

11.5 Multiply Bonded Organic Molecules

11.6 Hybridization of Atoms with More than an Octet of Electrons

11.7 Relative Energy Levels of The s-p Type of Hybrid Orbital

11.8 Localized Molecular Orbitals

11.9 Properties of Covalent Bonds

11.10 Resonance and Delocalized p Electrons

11.11 Delocalization Or Resonance Energy

Problems

Additional Problems

12: Intermolecular Forces

12.1 Dipole-Dipole Interaction

12.2 Ion-Dipole Attractions

12.3 Hydrogen Bonding

12.4 London Forces

12.5 London Forces and Molecular Shape

12.6 Van Der Waals Radii

Problems

13: Solutions

13.1 Introduction

13.2 Liquid Solutions

13.3 Saturation: Gases in Liquids

13.4 Saturation: Solids in Liquids Or Liquids in Liquids

13.5 Dependence of Solubility on Temperature and Pressure

13.6 Supersaturation

13.7 Solubility and Molecular Structure

13.8 Detergency

13.9 Solid Solutions

13.10 Measures of Composition for Solutions

Vapor Pressures of Solutions

13.11 General Remarks

13.12 Raoult's Law

13.13 Deviations from Raoult's Law

13.14 Activity

13.15 Henry's Law

13.16 Vapor Pressure and Equilibrium

13.17 Deliquescence

Colligative Properties of Solutions

13.18 Vapor Pressure Depression

13.19 Boiling-Point Elevation and Freezing-Point Depression

13.20 Osmotic Pressure

13.21 Determination of Molecular Weights

Problems

Additional Problems

14: Chemical Equilibrium

14.1 Introduction

14.2 Equilibrium in Gases

14.3 The Sulfur Dioxide-Sulfur Trioxide Equilibrium

14.4 Change of Κ with Form of Equation

14.5 Combination of Equilibria

14.6 The Equilibrium Condition in Terms of Concentrations

14.7 Principle of Le Châtelier

14.8 Equilibrium and Catalysis

14.9 Heterogeneous Equilibrium

14.10 Equilibrium in Solutions

14.11 The Distribution Law (Or Law of Partition)

14.12 Equilibrium Calculations

Problems

Additional Problems

15: Ionic Solutions

15.1 Electrical Conductance

15.2 Colligative Properties of Solutions of Electrolytes

15.3 Electronic Conduction

15.4 Ionic Conduction

15.5 Solvation of Ions

15.6 Dielectric Constant

15.7 Other Evidence for Ions

15.8 Covalent Electrolytes

15.9 Net Ionic Equations

15.10 Balancing Oxidation-Reduction Equations by the Ion-Electron Method

15.11 Electrode Processes

15.12 Electrolysis of Fused Salts

15.13 Faraday’s Laws

15.14 Measurement of Conductivity

15.15 Equivalent Conductance

15.16 Change of Equivalent Conductance with Concentration

15.17 Strong Electrolytes

15.18 Conductances of Individual Ions

15.19 Association in Strong Electrolytes

15.20 Weak Electrolytes

15.21 Degree of Dissociation

15.22 Activities of Electrolytes

15.23 Activity and Interionic Forces

Problems

Additional Problems

16: Galvanic Cells and The Driving Force of Chemical Reactions

16.1 Introduction

16.2 Electricity From a Chemical Reaction

16.3 A Galvanic Cell with One Solution

16.4 Electrical Work

16.5 Measurement of Electromotive Force

16.6 Free Energy and Entropy

16.7 Cells with Liquid Junctions

16.8 Conventional Notation for Cells

16.9 The Hydrogen Half-Cell; Concentration Cells

16.10 The Sign of an Electrode

16.11 The Nernst Equation

16.12 Dependence of E.M.F. on Concentrations

16.13 Determination of Standard E.M.F. and Activity Coefficients

16.14 Half-Cell Potentials

16.15 Calculation of Equilibrium Constants

16.16 Free Energy and Equilibrium

16.17 Predicting The Direction of a Reaction

16.18 Oxidation and Reduction Potentials

16.19 Decomposition Potential; Overvoltage and Polarization

16.20 Selection of Electrode Process

16.21 The Dry Cell and The Storage Cell

16.22 Corrosion

Problems

Additional Problems

17: Acids and Bases

17.1 Nomenclature of Oxyacids and Their Anions

17.2 Early Definitions

17.3 Brönsted-Lowry Concept of Acid-Base Reactions

17.4 Amphoterism; Autoprotolysis (Self-Ionization)

17.5 Types of Protolytic Reaction

17.6 Protolysis in Nonaqueous Media

17.7 Lewis Acid-Base Concept

17.8 Examples of Lewis Acids

17.9 Mechanism of Proton Transfer

17.10 Energetics of Acid Dissociation

17.11 Industrial Applications of Acid-Base Reactions

Problems

Additional Problems

18: Hydrides and Oxides; Structure and Basicity

18.1 Reactivity of Hydrides

18.2 The Periodicity of Properties of The Oxides

18.3 Structure of Oxyanions; p-dπ Bondin

18.4 Relationship of Structure To Acidity and Basicity

18.5 Charge Dispersal and Basicity

18.6 Effect of Anionic Charge

18.7 s Character and Basicity

18.8 Inductive Effect and Basicity

18.9 Preparation of Acids

Problems

19: Calculations of Ionic Equilibrium

Acid-Base Equilibria

19.1 The Ionization of Water

19.2 pH and pOH

19.3 Acidic, Basic, and Neutral Solutions

19.4 Ionization of Weak Acids

19.5 Ionization of Weak Bases

19.6 Conjugate Acid-Base Pairs

19.7 Charged Acids and Bases

19.8 Polyprotic Acids and Bases

19.9 Weak Acid (Or Base) in The Presence of Strong Acid (Or Base)

19.10 Buffer Solutions

19.11 Indicators

Slightly Soluble Salts and Complex Ions

19.12 Solubility Products

19.13 Effect of Ph on Solubility

19.14 Complex Ions

19.15 Effect of Complex-Ion Formation on Solubility

Calculations Using Activities

19.16 Activity Coefficients

19.17 Ionic Strength

19.18 Calculation of Activity Coefficients

19.19 Application of Activity Coefficients to Equilibrium Calculations

Problems

Additional Problems

20: Chemistry of the Common Cations and Anions: Background for Qualitative Inorganic Analysis

20.1 Solubility of Salts

20.2 Summary of Solubilities of Inorganic Salts

20.3 Color

20.4 Washing Precipitates; Peptization

20.5 Qualitative Cation Analysis

20.6 Chemistry of the Cations

20.7 Qualitative Analysis of Anions

Problems

Additional Problems

21: Quantitative Analysis

21.1 Gravimetric Analysis

21.2 Volumetric Analysis; Titrations and Normality

21.3 Titration Curves

21.4 Calculation of Titration Curves

21.5 Combined Volumetric and Gravimetric Analysis

21.6 Precision and Accuracy

Problems

Additional Problems

22: Modern Approaches To Analytical Chemistry: Chromatography and Spectrometry

22.1 General

22.2 Criteria of Purity and Methods of Purification

22.3 Chromatographic Methods

22.4 Solid-Liquid Adsorption Chromatography

22.5 Liquid-Liquid Partition Chromatography

22.6 Gas Chromatography

22.7 Ion-Exchange Chromatography

22.8 Electrochromatography

22.9 Spectrometric Methods

22.10 an Example of Absorption Spectrometry: The Infrared Spectrum

Problems

23: Chemical Kinetics

23.1 Introduction

23.2 Conditions Affecting Reaction Rates

23.3 Theory of Reaction Rates

23.4 Mechanism of Reaction from Rate Equation

23.5 Molecularity of a Reaction

23.6 Catalysis

23.7 Half-Life for First Order Reactions

23.8 Chain Mechanism

Problems

Additional Problems

24: Molecular Geometry and Bonding; Symmetry

24.1 Introduction

24.2 Principal Factors Determining Molecular Shape

24.3 Principal Effect of a Lone Pair

24.4 Molecules Whose Central Atoms Use Unhybridized p Orbitals

24.5 Shapes of Multiple-Bonded Molecules

24.6 Secondary Effects; Modifications in Bond Angles

24.7 Deviated Bond Angles and Hybridization

24.8 Molecular Shape and Dipole Moments

24.9 Molecular Symmetry

24.10 Stereoisomerism

Problems

Additional Problems

25: Transition Metal Complexes

25.1 Complex Formation

25.2 Coordination Number or Ligancy

25.3 Werner's Coordination Theory

25.4 Nomenclature

25.5 Coordination Number and Shape

Bonding in Transition Metal Complexes

25.6 Valence Bond Theory

25.7 Crystal Field Theory

25.8 Geometrical Isomerism

Problems

Additional Problems

26: Reactions of Covalent Bonds

26.1 Decomposition

26.2 Displacement or Substitution Reactions

26.3 Nucleophilic Displacement on a δ-Bonded Atom

26.4 Nucleophilic Displacement on a δ-Bonded Carbon Atom

26.5 Nucleophilic Displacement on Atoms Able to Acquire More than an Octet of Electrons

26.6 Nucleophilic Displacement on π-Bonded Atoms

26.7 Electrophilic Displacement on δ-Bonded Atoms

26.8 Electrophilic Displacement on π-Bonded Atoms

26.9 Free Radical Substitutions

26.10 Rearrangements

Problems

Additional Problems

27: Metals and Metallurgy

27.1 The Properties of Metals

27.2 The Metallic Bond; Early Ideas of the "Electron Gas"

27.3 The Band Theory of Metals

27.4 Metallic Properties in Terms of the Band Theory

27.5 Insulators and Semiconductors

27.6 Metallic Valence

27.7 Periodicity of Heats of Fusion and Vaporization of Metals and Nonmetals

27.8 Periodicity of Electrical and Thermal Conductivities of Metals and Nonmetals

27.9 Allotropy and Metallic Character

Metallurgical Processes

27.10 Sources of Metals: Thermodynamic Considerations

27.11 The Winning of Metals from Ores: General Considerations

27.12 Preliminary Physical Treatment

27.13 Physical Concentration

27.14 Chemical Leaching

27.15 Roasting: Thermodynamic Considerations

27.16 Reduction

27.17 Electrometallurgy

27.18 Refining: Electrolytic Method

27.19 Refining: Nonelectrolytic Methods

Problems

Additional Problems

28: Nuclear Chemistry

28.1 Radioactivity

28.2 Nuclear Energy

28.3 The Stability of Nuclei

28.4 Nuclear Reactions

28.5 Rate of Radioactive Decay Processes

28.6 Radiochemistry

28.7 Units for Reference

Problems

Additional Problems

29: Polymers

Background and Definitions

The Decomposition of Natural High Polymers; Monomeric Units (Mers)

The Production of Synthetic High Polymers; C-Polymerization

A-Polymerization

The Molecular Weight of Macromolecules

The Orientation of Monomeric Units in Macromolecules

Crystallinity of Polymers

Properties of Polymers

Biochemicals

Problems

Appendix I: Definitions and Review of Physical Concepts

Appendix II: Review of some Mathematical Operations

Appendix III: Bohr Theory of the Hydrogen Atom

Appendix IV: Fundamental Constants

Appendix V: Vapor Pressure of Water

Index