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  1. Preface
  2. 1 Essential Ideas
    1. Introduction
    2. 1.1 Chemistry in Context
    3. 1.2 Phases and Classification of Matter
    4. 1.3 Physical and Chemical Properties
    5. 1.4 Measurements
    6. 1.5 Measurement Uncertainty, Accuracy, and Precision
    7. 1.6 Mathematical Treatment of Measurement Results
    8. Key Terms
    9. Key Equations
    10. Summary
    11. Exercises
  3. 2 Atoms, Molecules, and Ions
    1. Introduction
    2. 2.1 Early Ideas in Atomic Theory
    3. 2.2 Evolution of Atomic Theory
    4. 2.3 Atomic Structure and Symbolism
    5. 2.4 Chemical Formulas
    6. Key Terms
    7. Key Equations
    8. Summary
    9. Exercises
  4. 3 Electronic Structure and Periodic Properties of Elements
    1. Introduction
    2. 3.1 Electromagnetic Energy
    3. 3.2 The Bohr Model
    4. 3.3 Development of Quantum Theory
    5. 3.4 Electronic Structure of Atoms (Electron Configurations)
    6. 3.5 Periodic Variations in Element Properties
    7. 3.6 The Periodic Table
    8. 3.7 Molecular and Ionic Compounds
    9. Key Terms
    10. Key Equations
    11. Summary
    12. Exercises
  5. 4 Chemical Bonding and Molecular Geometry
    1. Introduction
    2. 4.1 Ionic Bonding
    3. 4.2 Covalent Bonding
    4. 4.3 Chemical Nomenclature
    5. 4.4 Lewis Symbols and Structures
    6. 4.5 Formal Charges and Resonance
    7. 4.6 Molecular Structure and Polarity
    8. Key Terms
    9. Key Equations
    10. Summary
    11. Exercises
  6. 5 Advanced Theories of Bonding
    1. Introduction
    2. 5.1 Valence Bond Theory
    3. 5.2 Hybrid Atomic Orbitals
    4. 5.3 Multiple Bonds
    5. 5.4 Molecular Orbital Theory
    6. Key Terms
    7. Key Equations
    8. Summary
    9. Exercises
  7. 6 Composition of Substances and Solutions
    1. Introduction
    2. 6.1 Formula Mass
    3. 6.2 Determining Empirical and Molecular Formulas
    4. 6.3 Molarity
    5. 6.4 Other Units for Solution Concentrations
    6. Key Terms
    7. Key Equations
    8. Summary
    9. Exercises
  8. 7 Stoichiometry of Chemical Reactions
    1. Introduction
    2. 7.1 Writing and Balancing Chemical Equations
    3. 7.2 Classifying Chemical Reactions
    4. 7.3 Reaction Stoichiometry
    5. 7.4 Reaction Yields
    6. 7.5 Quantitative Chemical Analysis
    7. Key Terms
    8. Key Equations
    9. Summary
    10. Exercises
  9. 8 Gases
    1. Introduction
    2. 8.1 Gas Pressure
    3. 8.2 Relating Pressure, Volume, Amount, and Temperature: The Ideal Gas Law
    4. 8.3 Stoichiometry of Gaseous Substances, Mixtures, and Reactions
    5. 8.4 Effusion and Diffusion of Gases
    6. 8.5 The Kinetic-Molecular Theory
    7. 8.6 Non-Ideal Gas Behavior
    8. Key Terms
    9. Key Equations
    10. Summary
    11. Exercises
  10. 9 Thermochemistry
    1. Introduction
    2. 9.1 Energy Basics
    3. 9.2 Calorimetry
    4. 9.3 Enthalpy
    5. 9.4 Strengths of Ionic and Covalent Bonds
    6. Key Terms
    7. Key Equations
    8. Summary
    9. Exercises
  11. 10 Liquids and Solids
    1. Introduction
    2. 10.1 Intermolecular Forces
    3. 10.2 Properties of Liquids
    4. 10.3 Phase Transitions
    5. 10.4 Phase Diagrams
    6. 10.5 The Solid State of Matter
    7. 10.6 Lattice Structures in Crystalline Solids
    8. Key Terms
    9. Key Equations
    10. Summary
    11. Exercises
  12. 11 Solutions and Colloids
    1. Introduction
    2. 11.1 The Dissolution Process
    3. 11.2 Electrolytes
    4. 11.3 Solubility
    5. 11.4 Colligative Properties
    6. 11.5 Colloids
    7. Key Terms
    8. Key Equations
    9. Summary
    10. Exercises
  13. 12 Thermodynamics
    1. Introduction
    2. 12.1 Spontaneity
    3. 12.2 Entropy
    4. 12.3 The Second and Third Laws of Thermodynamics
    5. 12.4 Free Energy
    6. Key Terms
    7. Key Equations
    8. Summary
    9. Exercises
  14. 13 Fundamental Equilibrium Concepts
    1. Introduction
    2. 13.1 Chemical Equilibria
    3. 13.2 Equilibrium Constants
    4. 13.3 Shifting Equilibria: Le Châtelier’s Principle
    5. 13.4 Equilibrium Calculations
    6. Key Terms
    7. Key Equations
    8. Summary
    9. Exercises
  15. 14 Acid-Base Equilibria
    1. Introduction
    2. 14.1 Brønsted-Lowry Acids and Bases
    3. 14.2 pH and pOH
    4. 14.3 Relative Strengths of Acids and Bases
    5. 14.4 Hydrolysis of Salts
    6. 14.5 Polyprotic Acids
    7. 14.6 Buffers
    8. 14.7 Acid-Base Titrations
    9. Key Terms
    10. Key Equations
    11. Summary
    12. Exercises
  16. 15 Equilibria of Other Reaction Classes
    1. Introduction
    2. 15.1 Precipitation and Dissolution
    3. 15.2 Lewis Acids and Bases
    4. 15.3 Coupled Equilibria
    5. Key Terms
    6. Key Equations
    7. Summary
    8. Exercises
  17. 16 Electrochemistry
    1. Introduction
    2. 16.1 Review of Redox Chemistry
    3. 16.2 Galvanic Cells
    4. 16.3 Electrode and Cell Potentials
    5. 16.4 Potential, Free Energy, and Equilibrium
    6. 16.5 Batteries and Fuel Cells
    7. 16.6 Corrosion
    8. 16.7 Electrolysis
    9. Key Terms
    10. Key Equations
    11. Summary
    12. Exercises
  18. 17 Kinetics
    1. Introduction
    2. 17.1 Chemical Reaction Rates
    3. 17.2 Factors Affecting Reaction Rates
    4. 17.3 Rate Laws
    5. 17.4 Integrated Rate Laws
    6. 17.5 Collision Theory
    7. 17.6 Reaction Mechanisms
    8. 17.7 Catalysis
    9. Key Terms
    10. Key Equations
    11. Summary
    12. Exercises
  19. 18 Representative Metals, Metalloids, and Nonmetals
    1. Introduction
    2. 18.1 Periodicity
    3. 18.2 Occurrence and Preparation of the Representative Metals
    4. 18.3 Structure and General Properties of the Metalloids
    5. 18.4 Structure and General Properties of the Nonmetals
    6. 18.5 Occurrence, Preparation, and Compounds of Hydrogen
    7. 18.6 Occurrence, Preparation, and Properties of Carbonates
    8. 18.7 Occurrence, Preparation, and Properties of Nitrogen
    9. 18.8 Occurrence, Preparation, and Properties of Phosphorus
    10. 18.9 Occurrence, Preparation, and Compounds of Oxygen
    11. 18.10 Occurrence, Preparation, and Properties of Sulfur
    12. 18.11 Occurrence, Preparation, and Properties of Halogens
    13. 18.12 Occurrence, Preparation, and Properties of the Noble Gases
    14. Key Terms
    15. Summary
    16. Exercises
  20. 19 Transition Metals and Coordination Chemistry
    1. Introduction
    2. 19.1 Occurrence, Preparation, and Properties of Transition Metals and Their Compounds
    3. 19.2 Coordination Chemistry of Transition Metals
    4. 19.3 Spectroscopic and Magnetic Properties of Coordination Compounds
    5. Key Terms
    6. Summary
    7. Exercises
  21. 20 Nuclear Chemistry
    1. Introduction
    2. 20.1 Nuclear Structure and Stability
    3. 20.2 Nuclear Equations
    4. 20.3 Radioactive Decay
    5. 20.4 Transmutation and Nuclear Energy
    6. 20.5 Uses of Radioisotopes
    7. 20.6 Biological Effects of Radiation
    8. Key Terms
    9. Key Equations
    10. Summary
    11. Exercises
  22. 21 Organic Chemistry
    1. Introduction
    2. 21.1 Hydrocarbons
    3. 21.2 Alcohols and Ethers
    4. 21.3 Aldehydes, Ketones, Carboxylic Acids, and Esters
    5. 21.4 Amines and Amides
    6. Key Terms
    7. Summary
    8. Exercises
  23. A | The Periodic Table
  24. B | Essential Mathematics
  25. C | Units and Conversion Factors
  26. D | Fundamental Physical Constants
  27. E | Water Properties
  28. F | Composition of Commercial Acids and Bases
  29. G | Standard Thermodynamic Properties for Selected Substances
  30. H | Ionization Constants of Weak Acids
  31. I | Ionization Constants of Weak Bases
  32. J | Solubility Products
  33. K | Formation Constants for Complex Ions
  34. L | Standard Electrode (Half-Cell) Potentials
  35. M | Half-Lives for Several Radioactive Isotopes
  36. Answer Key
    1. Chapter 1
    2. Chapter 2
    3. Chapter 3
    4. Chapter 4
    5. Chapter 5
    6. Chapter 6
    7. Chapter 7
    8. Chapter 8
    9. Chapter 9
    10. Chapter 10
    11. Chapter 11
    12. Chapter 12
    13. Chapter 13
    14. Chapter 14
    15. Chapter 15
    16. Chapter 16
    17. Chapter 17
    18. Chapter 18
    19. Chapter 19
    20. Chapter 20
    21. Chapter 21
  37. Index

5.1 Valence Bond Theory

1.

Explain how σ and π bonds are similar and how they are different.

2.

Use valence bond theory to explain the bonding in F2, HF, and ClBr. Sketch the overlap of the atomic orbitals involved in the bonds.

3.

Use valence bond theory to explain the bonding in O2. Sketch the overlap of the atomic orbitals involved in the bonds in O2.

4.

How many σ and π bonds are present in the molecule HCN?

5.

A friend tells you N2 has three π bonds due to overlap of the three p-orbitals on each N atom. Do you agree?

6.

Draw the Lewis structures for CO2 and CO, and predict the number of σ and π bonds for each molecule.

(a) CO2

(b) CO

5.2 Hybrid Atomic Orbitals

7.

Why is the concept of hybridization required in valence bond theory?

8.

Give the shape that describes each hybrid orbital set:

(a) sp2

(b) sp3d

(c) sp

(d) sp3d2

9.

Explain why a carbon atom cannot form five bonds using sp3d hybrid orbitals.

10.

What is the hybridization of the central atom in each of the following?

(a) BeH2

(b) SF6

(c) PO43−PO43−

(d) PCl5

11.

A molecule with the formula AB3 could have one of four different shapes. Give the shape and the hybridization of the central A atom for each.

12.

Methionine, CH3SCH2CH2CH(NH2)CO2H, is an amino acid found in proteins. The Lewis structure of this compound is shown below. What is the hybridization type of each carbon, oxygen, the nitrogen, and the sulfur?

A Lewis structure is shown in which a carbon atom is single bonded to three hydrogen atoms and single bonded to a sulfur atom with two lone pairs of electrons. The sulfur atom is attached to a chain of four singly bonded carbon atoms, the first two of which are single bonded to two hydrogen atoms each, and the third of which is single bonded to a hydrogen atom and single bonded to a nitrogen atom which has one lone electron pair. The nitrogen atom is also single bonded to two hydrogen atoms. The fourth andfinal carbon in the chain is double bonded to an oxygen with two lone pairs of electrons and single bonded to an oxygen atom with two lone pairs of electrons. The second oxygen atom is single bonded to a hydrogen atom.
13.

Sulfuric acid is manufactured by a series of reactions represented by the following equations:
S8(s)+8O2(g)8SO2(g)S8(s)+8O2(g)8SO2(g)
2SO2(g)+O2(g)2SO3(g)2SO2(g)+O2(g)2SO3(g)
SO3(g)+H2O(l)H2SO4(l)SO3(g)+H2O(l)H2SO4(l)

Draw a Lewis structure, predict the molecular geometry by VSEPR, and determine the hybridization of sulfur for the following:

(a) circular S8 molecule

(b) SO2 molecule

(c) SO3 molecule

(d) H2SO4 molecule (the hydrogen atoms are bonded to oxygen atoms)

14.

Two important industrial chemicals, ethene, C2H4, and propene, C3H6, are produced by the steam (or thermal) cracking process:

2C3H8(g)C2H4(g)+C3H6(g)+CH4(g)+H2(g)2C3H8(g)C2H4(g)+C3H6(g)+CH4(g)+H2(g)

For each of the four carbon compounds, do the following:

(a) Draw a Lewis structure.

(b) Predict the geometry about the carbon atom.

(c) Determine the hybridization of each type of carbon atom.

15.

Analysis of a compound indicates that it contains 77.55% Xe and 22.45% F by mass.

(a) What is the empirical formula for this compound? (Assume this is also the molecular formula in responding to the remaining parts of this exercise).

(b) Write a Lewis structure for the compound.

(c) Predict the shape of the molecules of the compound.

(d) What hybridization is consistent with the shape you predicted?

16.

Consider nitrous acid, HNO2 (HONO).

(a) Write a Lewis structure.

(b) What are the electron pair and molecular geometries of the internal oxygen and nitrogen atoms in the HNO2 molecule?

(c) What is the hybridization on the internal oxygen and nitrogen atoms in HNO2?

17.

Strike-anywhere matches contain a layer of KClO3 and a layer of P4S3. The heat produced by the friction of striking the match causes these two compounds to react vigorously, which sets fire to the wooden stem of the match. KClO3 contains the ClO3ClO3 ion. P4S3 is an unusual molecule with the skeletal structure.

A Lewis structure is shown in which three phosphorus atoms are single bonded together to form a triangle. Each phosphorus is bonded to a sulfur atom by a vertical single bond and each of those sulfur atoms is then bonded to a single phosphorus atom so that a six-sided ring is created with a sulfur in the middle.

(a) Write Lewis structures for P4S3 and the ClO3ClO3 ion.

(b) Describe the geometry about the P atoms, the S atom, and the Cl atom in these species.

(c) Assign a hybridization to the P atoms, the S atom, and the Cl atom in these species.

(d) Determine the oxidation states and formal charge of the atoms in P4S3 and the ClO3ClO3 ion.

18.

Identify the hybridization of each carbon atom in the following molecule. (The arrangement of atoms is given; you need to determine how many bonds connect each pair of atoms.)

A Lewis structure is shown that is missing all of its bonds. Six carbon atoms form a chain. There are three hydrogen atoms located around the first carbon, two located around the second, one located near the fifth, and two located around the sixth carbon.
19.

Write Lewis structures for NF3 and PF5. On the basis of hybrid orbitals, explain the fact that NF3, PF3, and PF5 are stable molecules, but NF5 does not exist.

20.

In addition to NF3, two other fluoro derivatives of nitrogen are known: N2F4 and N2F2. What shapes do you predict for these two molecules? What is the hybridization for the nitrogen in each molecule?

5.3 Multiple Bonds

21.

The bond energy of a C–C single bond averages 347 kJ mol−1; that of a CCCC triple bond averages 839 kJ mol−1. Explain why the triple bond is not three times as strong as a single bond.

22.

For the carbonate ion, CO32−,CO32−, draw all of the resonance structures. Identify which orbitals overlap to create each bond.

23.

A useful solvent that will dissolve salts as well as organic compounds is the compound acetonitrile, H3CCN. It is present in paint strippers.

(a) Write the Lewis structure for acetonitrile, and indicate the direction of the dipole moment in the molecule.

(b) Identify the hybrid orbitals used by the carbon atoms in the molecule to form σ bonds.

(c) Describe the atomic orbitals that form the π bonds in the molecule. Note that it is not necessary to hybridize the nitrogen atom.

24.

For the molecule allene, H2C=C=CH2,H2C=C=CH2, give the hybridization of each carbon atom. Will the hydrogen atoms be in the same plane or perpendicular planes?

25.

Identify the hybridization of the central atom in each of the following molecules and ions that contain multiple bonds:

(a) ClNO (N is the central atom)

(b) CS2

(c) Cl2CO (C is the central atom)

(d) Cl2SO (S is the central atom)

(e) SO2F2 (S is the central atom)

(f) XeO2F2 (Xe is the central atom)

(g) ClOF2+ClOF2+ (Cl is the central atom)

26.

Describe the molecular geometry and hybridization of the N, P, or S atoms in each of the following compounds.

(a) H3PO4, phosphoric acid, used in cola soft drinks

(b) NH4NO3, ammonium nitrate, a fertilizer and explosive

(c) S2Cl2, disulfur dichloride, used in vulcanizing rubber

(d) K4[O3POPO3], potassium pyrophosphate, an ingredient in some toothpastes

27.

For each of the following molecules, indicate the hybridization requested and whether or not the electrons will be delocalized:

(a) ozone (O3) central O hybridization

(b) carbon dioxide (CO2) central C hybridization

(c) nitrogen dioxide (NO2) central N hybridization

(d) phosphate ion (PO43−)(PO43−) central P hybridization

28.

For each of the following structures, determine the hybridization requested and whether the electrons will be delocalized:

(a) Hybridization of each carbon

A Lewis structure is shown in which a carbon atom is single bonded to three hydrogen atoms and a second carbon atom. This second carbon atom is, in turn, double bonded to an oxygen atom with two lone pairs of electrons. The second carbon atom is also single bonded to another carbon atom that is single bonded to three hydrogen atoms.

(b) Hybridization of sulfur

A Lewis structure is shown in which a sulfur atom with two lone pairs of electrons and a positive sign is double bonded to an oxygen with two lone pairs of electrons. The sulfur atom is also single bonded to an oxygen with three lone pairs of electrons with a negative sign. It is drawn in an angular shape.

(c) All atoms

A Lewis structure is shown in which a hexagonal ring structure is made up of five carbon atoms and one nitrogen atom with a lone pair of electrons. There are alternating double and single bonds in between each carbon atom. Each carbon atom is also single bonded to one hydrogen atom.
29.

Draw the orbital diagram for carbon in CO2 showing how many carbon atom electrons are in each orbital.

5.4 Molecular Orbital Theory

30.

Sketch the distribution of electron density in the bonding and antibonding molecular orbitals formed from two s orbitals and from two p orbitals.

31.

How are the following similar, and how do they differ?

(a) σ molecular orbitals and π molecular orbitals

(b) ψ for an atomic orbital and ψ for a molecular orbital

(c) bonding orbitals and antibonding orbitals

32.

If molecular orbitals are created by combining five atomic orbitals from atom A and five atomic orbitals from atom B combine, how many molecular orbitals will result?

33.

Can a molecule with an odd number of electrons ever be diamagnetic? Explain why or why not.

34.

Can a molecule with an even number of electrons ever be paramagnetic? Explain why or why not.

35.

Why are bonding molecular orbitals lower in energy than the parent atomic orbitals?

36.

Calculate the bond order for an ion with this configuration:

(σ2s)2(σ2s*)2(σ2px)2(π2py,π2pz)4(π2py*,π2pz*)3(σ2s)2(σ2s*)2(σ2px)2(π2py,π2pz)4(π2py*,π2pz*)3
37.

Explain why an electron in the bonding molecular orbital in the H2 molecule has a lower energy than an electron in the 1s atomic orbital of either of the separated hydrogen atoms.

38.

Predict the valence electron molecular orbital configurations for the following, and state whether they will be stable or unstable ions.

(a) Na22+Na22+

(b) Mg22+Mg22+

(c) Al22+Al22+

(d) Si22+Si22+

(e) P22+P22+

(f) S22+S22+

(g) F22+F22+

(h) Ar22+Ar22+

39.

Determine the bond order of each member of the following groups, and determine which member of each group is predicted by the molecular orbital model to have the strongest bond.

(a) H2, H2+,H2+, H2H2

(b) O2, O22+,O22+, O22−O22−

(c) Li2, Be2+,Be2+, Be2

(d) F2, F2+,F2+, F2F2

(e) N2, N2+,N2+, N2N2

40.

For the first ionization energy for an N2 molecule, what molecular orbital is the electron removed from?

41.

Compare the atomic and molecular orbital diagrams to identify the member of each of the following pairs that has the highest first ionization energy (the most tightly bound electron) in the gas phase:

(a) H and H2

(b) N and N2

(c) O and O2

(d) C and C2

(e) B and B2

42.

Which of the period 2 homonuclear diatomic molecules are predicted to be paramagnetic?

43.

A friend tells you that the 2s orbital for fluorine starts off at a much lower energy than the 2s orbital for lithium, so the resulting σ2s molecular orbital in F2 is more stable than in Li2. Do you agree?

44.

True or false: Boron contains 2s22p1 valence electrons, so only one p orbital is needed to form molecular orbitals.

45.

What charge would be needed on F2 to generate an ion with a bond order of 2?

46.

Predict whether the MO diagram for S2 would show s-p mixing or not.

47.

Explain why N22+N22+ is diamagnetic, while O24+,O24+, which has the same number of valence electrons, is paramagnetic.

48.

Using the MO diagrams, predict the bond order for the stronger bond in each pair:

(a) B2 or B2+B2+

(b) F2 or F2+F2+

(c) O2 or O22+O22+

(d) C2+C2+ or C2C2

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