Ebook PDF Chemistry A Molecular Approach Third 3rd Canadian Edition PDF
Ebook PDF Chemistry A Molecular Approach Third 3rd Canadian Edition PDF
Ebook PDF Chemistry A Molecular Approach Third 3rd Canadian Edition PDF
1 18
1 2
1 H He
Metals Metalloids Nonmetals
1.008 2 13 14 15 16 17 4.003
3 4 5 6 7 8 9 10
2 Li Be B C N O F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18
Transition metals
11 12 13 14 15 16 17 18
3 Na Mg Al Si P S Cl Ar
22.99 24.31 3 4 5 6 7 8 9 10 11 12 26.98 28.09 30.97 32.07 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.87 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.38 69.72 72.64 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.96 [98] 101.07 102.91 106.42 107.87 112.41 114.82 118.71 121.76 127.60 126.90 131.29
55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.91 137.33 178.49 180.95 183.84 186.21 190.23 192.22 195.08 196.97 200.59 204.38 207.2 208.98 [208.98] [209.99] [222.02]
87 88 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
7 Fr Ra Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
[223.02] [226.03] [261.11] [262.11] [266.12] [264.12] [269.13] [268.14] [271] [272] [277] [286] [289] [289] [292] [294] [294]
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
Lanthanoid series La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
138.91 140.12 140.91 144.24 [145] 150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.05 174.97
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
Actinoid series Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
[227.03] 232.04 231.04 238.03 [237.05] [244.06] [243.06] [247.07] [247.07] [251.08] [252.08] [257.10] [258.10] [259.10] [262.11]
Atomic masses in brackets are the masses of the longest-lived or most important isotope of radioactive elements.
xii Contents
12
Determining the Order of a Reaction 546 Reaction
Order for Multiple Reactants 548
Solutions 491 13.4 The Integrated Rate Law: The Dependence of
12.1 Thirsty Solutions: Why You Shouldn’t Drink Seawater 491 Concentration on Time 549
12.2 Types of Solutions and Solubility 493 Half-Life, Lifetime, and Decay Time 554
Nature’s Tendency Toward Mixing: 13.5 The Effect of Temperature on Reaction Rate 557
Entropy 493 The Effect of Intermolecular Arrhenius Plots: Experimental Measurements
Forces 494 of the Frequency Factor and the Activation
Chemistry in Your Day: Vitamin D in Foods Energy 560 The Collision Model: A Closer Look
and Supplements 497 at the Frequency Factor 562
12.3 Energetics of Solution Formation 498 13.6 Reaction Mechanisms 564
Aqueous Solutions and Heats of Hydration 500 Rate Laws for Elementary Steps 565
12.4 Solution Equilibrium and Factors Affecting Solubility 501 Rate-Determining Steps and Overall
Reaction Rate Laws 565 The Steady-State
The Temperature Dependence of the Solubility of
Approximation 568
Solids 502 Factors Affecting the Solubility of
Gases in Water 503 13.7 Catalysis 571
12.5 Expressing Solution Concentration 506 Homogeneous and Heterogeneous
Catalysis 572 Enzymes: Biological Catalysts 574
Chemistry in the Environment: Lake Nyos 506
Chemistry and Medicine: Enzyme Catalysis and
Molarity 507 Molality 508 Parts by Mass and
the Role of Chymotrypsin in Digestion 577
Parts by Volume 508 Mole Fraction and Mole
Percent 510 Chapter in Review 578
Chemistry in the Environment: Pharmaceuticals Key Terms 578 Key Concepts 578 Key Equations
and Personal Care Products 510 and Relationships 579 Key Skills 579
14.4 The Equilibrium Constant (K) 601 Strong Acids 652 Weak Acids 652 Percent
Units of Equilibrium Constants 601 Ionization of a Weak Acid 657 Mixtures of
The Significance of the Equilibrium Acids 658 Finding the [OH-] and pH of Basic
Constant 601 Relationships Between the Solutions 660
Equilibrium Constant and the Chemical 15.8 The Acid–Base Properties of Ions and Salts 662
Equation 602 Anions as Weak Bases 663 Cations as Weak
Chemistry and Medicine: Life and Equilibrium 603 Acids 666 Classifying Salt Solutions as Acidic,
14.5 Calculating the Equilibrium Constant from Basic, or Neutral 667
Measured Quantities 605 15.9 Polyprotic Acids 670
14.6 The Reaction Quotient: Predicting the Finding the pH of Polyprotic Acid
Direction of Change 608 Solutions 671 Finding the Concentration of the
Anions for a Weak Diprotic Acid Solution 673
14.7 Finding Equilibrium Concentrations 610
Chemistry in Your Day: Weak Acids in Wine 674
Finding Partial Pressures or Concentrations at
Equilibrium Amounts When We Know the 15.10 Lewis Acids and Bases 675
Equilibrium Constant and All But One of the Molecules That Act as Lewis Acids 676 Cations
Equilibrium Amounts of the Reactants and That Act as Lewis Acids 677
Products 610 Finding Equilibrium Concentrations 15.11 Strengths of Acids and Bases and Molecular Structure 677
When We Know the Equilibrium Constant and Initial Binary Acids 677 Oxyacids 678 Amine
Concentrations or Pressures 611 Simplifying Bases 680
Approximations in Working Equilibrium
Problems 615 15.12 Ocean Acidification 680
14.8 Le Châtelier’s Principle: How a System Chapter in Review 682
at Equilibrium Responds to Disturbances 619 Key Terms 682 Key Concepts 682 Key Equations and
Relationships 683 Key Skills 683
The Effect of Changing the Amount of Reactant
or Product on Equilibrium 619 The Effect of a Exercises 684
Volume Change on Equilibrium 622 The Effect Review Questions 684 Problems by Topic 685
of Changing the Pressure by Adding an Inert Cumulative Problems 688 Challenge Problems 690
Gas 623 The Effect of a Temperature Change Conceptual Problems 690
on Equilibrium 623
Chapter in Review
Key Terms 626 Key Concepts 626
Relationships 627 Key Skills 627
Key Equations and
626
16 Aqueous Ionic Equilibrium
16.1 The Danger of Antifreeze
691
692
Exercises 628
Review Questions 628 Problems by Topic 629
16.2 Buffers: Solutions That Resist pH Change 693
Cumulative Problems 633 Challenge Problems 634 Calculating the pH of a Buffer Solution 694 The
Conceptual Problems 635 Henderson–Hasselbalch Equation 695 Calculating
pH Changes in a Buffer Solution 698 Buffers
15
Containing a Base and Its Conjugate Acid 701
16.3 Buffer Effectiveness: Buffer Range and
Acids and Bases 636 Buffer Capacity 703
15.1 Heartburn 636 Relative Amounts of Acid and Base 703 Absolute
15.2 The Nature of Acids and Bases 637 Concentrations of the Acid and Conjugate
Base 703 Buffer Range 704
15.3 Definitions of Acids and Bases 639
The Arrhenius Definition 639 The Brønsted–Lowry Chemistry and Medicine: Buffer Effectiveness
Definition 640 in Human Blood 705
15.4 Acid Strength and the Acid Ionization Constant (Ka) 642 Buffer Capacity 706
Strong Acids 642 Weak Acids 643 The Acid 16.4 Titrations and pH Curves 706
Ionization Constant (Ka) 644 The Titration of a Strong Acid with a Strong
15.5 Base Solutions 645 Base 706 The Titration of a Weak Acid with a
Strong Base 711 The Titration of a Weak Base with
Strong Bases 645 Weak Bases 645
a Strong Acid 716 The Titration of a Polyprotic
15.6 Autoionization of Water and pH 647 Acid 717 Indicators: pH-Dependent Colours 717
The pH Scale: A Way to Quantify Acidity and 16.5 Solubility Equilibria and the Solubility
Basicity 649 pOH and Other p Scales 650 Product Constant 720
Chemistry and Medicine: Ulcers 651 Ksp and Molar Solubility 720 Ksp and Relative
15.7 Finding [H3O+], [OH−], and pH of Acid or Solubility 723 The Effect of a Common Ion on
Base Solutions 652 Solubility 723
xiv C ontents
Chemistry and Medicine: Fluoride and Teeth 724 The Temperature Dependence of the Equilibrium
The Effect of an Uncommon Ion on Solubility Constant 783
(Salt Effect) 725 The Effect of pH on Solubility 726 Chapter in Review 785
16.6 Precipitation 727 Key Terms 785 Key Concepts 786 Key Equations
Selective Precipitation 729 and Relationships 786 Key Skills 787
16.7 Qualitative Chemical Analysis 730 Exercises 788
Group A: Insoluble Chlorides 731 Group B: Acid- Review Questions 788 Problems by Topic 788
Insoluble Sulfides 732 Group C: Base-Insoluble Cumulative Problems 791 Challenge Problems 793
Sulfides and Hydroxides 732 Group D: Insoluble Conceptual Problems 794
Phosphates 732 Group E: Alkali Metals
and NH4+ 732
16.8 Complex–Ion Equilibria
The Effect of Complex–Ion Equilibria on
733 18 Electrochemistry
18.1 Pulling the Plug on the Power Grid
795
796
Solubility 735
18.2 Voltaic (or Galvanic) Cells: Generating Electricity
Chapter in Review 736
from Spontaneous Chemical Reactions 796
Key Terms 736 Key Concepts 736 Key Equations
Electrochemical Cell Notation 799
and Relationships 737 Key Skills 737
Exercises
738
18.3 Standard Electrode Potentials 799
Predicting the Spontaneous Direction of an Oxidation–
Review Questions 738 Problems by Topic 738
Reduction Reaction 805 Predicting Whether a Metal
Cumulative Problems 743 Challenge Problems 744
Will Dissolve in Acid 808
Conceptual Problems 745
18.4 Cell Potential, Gibbs Energy,
and the Equilibrium Constant 808
17 Gibbs Energy
and Thermodynamics
17.1 Spontaneous and Nonspontaneous Processes
746
747
The Relationship Between ¢rG° and
812
Concentration Cells 816
17.2 Entropy and the Second Law of Thermodynamics 748 Chemistry and Medicine: Concentration Cells in
Entropy 750 The Entropy Change Associated Human Nerve Cells 819
with a Change in State 754
18.6 Batteries: Using Chemistry to Generate Electricity 819
17.3 Heat Transfer and Changes in the Entropy of the Dry-Cell Batteries 819 Lead–Acid
Surroundings 755 Storage Batteries 820 Other Rechargeable
The Temperature Dependence of ¢Ssurr 757 Batteries 820 Fuel Cells 822
Quantifying Entropy Changes in the Surroundings 757 Chemistry in Your Day: Rechargeable Battery
17.4 Entropy Changes for Phase Transitions 759 Recycling 823
17.5 Entropy Changes in Chemical Reactions: 18.7 Electrolysis: Driving Nonspontaneous
Calculating ¢rS° 760 Chemical Reactions with Electricity 823
Standard Molar Entropies (S°) and the Third Law of Predicting the Products of
Thermodynamics 760 Electrolysis 826 Stoichiometry of Electrolysis 829
17.6 Gibbs Energy 765 18.8 Corrosion: Undesirable Redox Reactions 831
The Effect of ¢r H, ¢r S, and T on Spontaneity 766 Preventing Corrosion 833
17.7 Gibbs Energy Changes in Chemical Reactions: Chapter in Review 833
Calculating ¢rG° 769 Key Terms 833 Key Concepts 833 Key Equations and
Calculating Gibbs Energy Changes with Relationships 834 Key Skills 835
¢rG° = ¢rH° - T ¢rS° 769 Calculating ¢rG° with Exercises 835
Tabulated Values of Gibbs Energies of Formation 771 Review Questions 835 Problems by Topic 836
Calculating ¢rG° for a Stepwise Reaction from the Cumulative Problems 839 Challenge Problems 841
Changes in Gibbs Energy for Each of the Steps 772 Conceptual Problems 841
17.8 Making a Nonspontaneous Process Spontaneous 773
17.9 What Is Gibbs Energy? 776
17.10 Gibbs Energy Changes for Nonstandard States: The
Relationship Between ¢rG° and ¢rG
The Gibbs Energy Change of a Reaction Under
777
19 Radioactivity and
Nuclear Chemistry
19.1 Medical Isotopes
842
842
Nonstandard Conditions 777
17.11 Gibbs Energy and Equilibrium: Relating ¢rG° to the 19.2 The Discovery of Radioactivity 843
Equilibrium Constant (K ) 781 19.3 Types of Radioactivity 844
C ontents xv
Alpha (a) Decay 845 Beta (b) Decay 846 20.5 Constitutional Isomerism 893
Gamma (g) Ray Emission 847 20.6 Stereoisomerism I: Conformational Isomerism 894
Positron Emission 847 Electron Capture 847
Conformational Isomerism: Rotation About
19.4 The Valley of Stability: Predicting the Single Bonds 894 Ring Conformations of
Type of Radioactivity 849 Cycloalkanes 896
Magic Numbers 851 Radioactive Decay 20.7 Stereoisomerism II: Configurational Isomerism 897
Series 851
Cis–Trans Isomerism in Alkenes 898 Enantiomers:
19.5 Measurements and Units of Radioactivity 851 Chirality 901 Absolute Configurations 903
19.6 The Kinetics of Radioactive Decay and Chemistry and Medicine: Anesthetics and Alcohol 905
Radiometric Dating 852 20.8 Structure Determination 905
The Integrated Rate Law 853 Radiocarbon Dating: Using the Molecular Formula: The Index of Hydrogen
Using Radioactivity to Measure the Age of Fossils and Deficiency 905 Spectroscopic Methods for Structure
Artifacts 856 Uranium/Lead Dating 857 Determination 908
19.7 The Discovery of Fission: The Atomic Bomb Chapter in Review 911
and Nuclear Power 859 Key Terms 911 Key Concepts 911 Key Equations
Nuclear Power: Using Fission to Generate and Relationships 912 Key Skills 913
Electricity 860
Exercises 913
Chemistry in Your Day: Uranium Isotopes Review Questions 913 Problems by Topic 914
and the CANDU Reactor 862 Cumulative Problems 916 Challenge Problems 917
19.8 Converting Mass to Energy in Nuclear Reactions and Conceptual Problems 918
Nuclear Binding Energy 862
21
Nuclear Binding Energy 863
19.9 Nuclear Fusion: The Power of the Sun 865 Organic Chemistry II: Reactions 920
19.10 Nuclear Transmutation and Transuranium Elements 866
21.1 Discovering New Drugs 921
19.11 The Effects of Radiation on Life 868
21.2 Organic Acids and Bases 921
Acute Radiation Damage 868 Increased Cancer
Risk 868 Genetic Defects 868 Measuring The Range of Organic Acidities 921 Inductive
Radiation Exposure 868 Effects: Withdrawal of Electron Density 923
Resonance Effects: Charge Delocalization in
19.12 Radioactivity in Medicine and Other Applications 870 the Conjugate Base 924 Acidic Hydrogen
Diagnosis in Medicine 870 Radiotherapy in Atoms Bonded to Carbon 925 Mechanisms
Medicine 871 Other Applications 871 in Organic Chemistry 925 Acid and Base
Chapter in Review 872 Reagents 926
Key Terms 872 Key Concepts 872 Key Equations 21.3 Oxidation and Reduction 928
and Relationships 873 Key Skills 873 Redox Reactions 929
Exercises 874 Chemistry in Your Day: Hydrogen
Review Questions 874 Problems by Topic 874 and the Oil Sands 931
Cumulative Problems 876 Challenge Problems 877
21.4 Nucleophilic Substitution Reactions at
Conceptual Problems 877
Saturated Carbon 932
20
The SN1 Mechanism 932 The SN2
Mechanism 934 Factors Affecting Nucleophilic
Organic Chemistry I: Structures 878 Substitution Reactions 935
21.5 Elimination Reactions 938
20.1 Fragrances and Odours 879
The E1 Mechanism 939 The E2
20.2 Carbon: Why It Is Unique 879 Mechanism 940 Elimination Versus
The Nature of Science: Vitalism and the Substitution 940
Perceived Difference Between Organic and 21.6 Electrophilic Additions to Alkenes 940
Inorganic880
Hydrohalogenation 940 Other Addition
20.3 Hydrocarbons 881 Reactions 941
Drawing Hydrocarbon Structures 881 Types of 21.7 Nucleophilic Additions to Aldehydes and Ketones 942
Hydrocarbons 884 Alkanes 884 Alkenes 885
Addition of Alcohols 942 The Grignard
Alkynes 885 Conjugated Alkenes and
Reaction 943
Aromatics 886
21.8 Nucleophilic Substitutions of Acyl Compounds 945
20.4 Functional Groups 887
21.9 Electrophilic Aromatic Substitutions 949
Halides 888 Amines 888 Alcohols 889
Ethers 890 Carbonyls: Aldehydes and Ketones 890 21.10 Polymerization 950
The Carboxylic Acid Family 891 Step-Growth Polymers 951 Addition Polymers 951
xvi C ontents
Chemistry in Your Day: High-, Medium-, and 23.4 Boron and Its Remarkable Structures 1006
Low-Density Polyethylene 952 Elemental Boron 1006 Boron–Halogen
Chapter in Review 953 Compounds: Trihalides 1007 Boron–Oxygen
Key Terms 953 Key Concepts 954 Key Equations and Compounds 1008 Boron–Hydrogen Compounds:
Relationships 955 Key Skills 956 Boranes 1008
22 Biochemistry
22.1 Diabetes and the Synthesis of Human Insulin
966
966
Compounds 1016 Phosphorus Compounds 1019
23.7 Oxygen
Elemental Oxygen 1021 Uses for
1021
across North America. So, why do we need a Canadian edi- units keeps students from getting into unit troubles when doing
tion? The short answer is that general chemistry courses in thermodynamic calculations.
Canada are different from those in the United States. First-year Explicitly, we have provided the distinctions and connec-
chemistry curricula in Canada are generally at a higher level tions between the unitless thermodynamic equilibrium con-
than what is seen south of the border. There is a need for a stant, Keq or simply K, and the phenomenological equilibrium
strong chemistry textbook that serves Canadian general chem- constants, Kc and KP, which can have units in terms of con-
istry courses. centration and pressure, respectively, again in accordance with
The Canadian adaptation of Chemistry: A Molecular IUPAC recommendations. This is done in the most basic of
Approach drew very heavily on feedback from professors and terms, assuming that gases and solutions are ideal so that their
instructors across Canada. As the Canadian authors, we took partial pressures and concentrations are assumed to be numeri-
the reviews and consultations very seriously and did our best to cally equivalent to their activities, setting up for a more rigor-
adapt Tro’s textbook accordingly. In general terms, the adapta- ous treatment in second-year analytical and physical chemistry
tion involved making the following changes. courses.
International Conventions on Units, Symbols, and Nomenclature Following recommendations set out by the IUPAC ensures
The field of chemistry is communicated according to conven- that we speak a common language—and teach a common lan-
tions that are determined by the broader international chemistry guage. Otherwise, students who go on in chemistry have to
community, through the International Union of Pure and Applied convert from the language learned in first year as soon as the
Chemistry (IUPAC). IUPAC continually releases recommen- very next year, when they take their first physical chemistry
dations on chemical nomenclature, definitions, symbols, and course.
units. IUPAC recommendations are not static; they may evolve Current Theories We have updated the text so that the
over time as new information comes to light. Although many most current, consensus scientific view is described. This is
textbooks state that they follow the recommendations of the most notable in the case of bonding theory and the so-called
IUPAC, you will find that the Canadian edition of Chemistry: A expanded octet. In this case, evidence shows that the d orbit-
Molecular Approach scrupulously follows IUPAC recommen- als have a negligible contribution to bonding, which means that
dations for chemical names and symbols, nomenclature, and full sp3d and sp3d2 hybridizations should no longer be included
conventions for symbols and units in measurements. In the case in bonding theories, even though this idea continues to appear
of chemical nomenclature, there are a number of non-IUPAC in general chemistry textbooks. This Canadian edition reflects
chemical names that are so common that we have to include the most current understanding of chemical phenomenon, at the
them along with the IUPAC recommended name. first-year level.
S.I. units of measurement are used exclusively. Imperial Organic Chemistry The coverage of organic chemistry has
units such as the gallon, pound, and the Fahrenheit scale of been expanded to two chapters, reflecting the curricula in many
temperature have not been used in modern science for over a Canadian universities, which provide additional organic chem-
generation. IUPAC recommended defining standard pressure istry coverage in first-year chemistry. The first organic chem-
as 1 bar (or 100 kPa) back in 1982. This is the standard that istry chapter covers structure and bonding, stereochemistry,
has been adopted by chemists worldwide and is almost exclu- and structure determination. The second chapter covers organic
sive in second-year physical chemistry texts. Only in first-year reactivity, and it is organized according to reaction mechanisms.
textbooks does the atmosphere still linger as standard pressure.
Canadian Context Naturally, a Canadian edition will include
In this text, standard pressure is the IUPAC-recommended bar.
Canadian examples. In some places, the Canadian content is
Students will see pressure in various units, but we make little
fun, like the hockey goalie’s “Quantum mechanical five hole”
use of the atmosphere. When dealing with ideal gases, the most
in Chapter 7. In other places, Canadian chemistry examples
common value of R is 0.08314 L bar mol−1 K−1.
are serious and important, like the chemistry of the oil sands.
In thermodynamics, we have adopted the recommended
Wherever Canadian content appears in this edition, it is there
notation for enthalpy, entropy, and Gibbs energy changes,
to promote student engagement. This book is meant for the
placing subscripts for changes after the delta sign rather than
Canadian student.
after H, S, or G. For example, the standard reaction enthalpy
is expressed as ¢rH° rather than ¢H°rxn. This is a subtle change End-of-Chapter Problems One of the first things that profes-
that matters. The type of change (¢) is marked on the ¢ symbol sors consider when choosing a chemistry textbook is the quality
(reaction, ¢r; formation, ¢f; and so on), rather than the type of of end-of-chapter problems. This is because, to learn chemistry,
thermodynamic quantity. We understand that this notation is students need to work through meaningful exercises and prob-
not used everywhere. However, we believe that students should lems. Tro’s Chemistry: A Molecular Approach has extensive,
use standard notation throughout their education. Students high-quality problems.
who continue in chemistry or other sciences will eventually First-year chemistry courses are perhaps the most impor-
come across the standard notation in physical chemistry text- tant courses in chemistry programs, because they lay the foun-
books and in places like the CRC Handbook of Chemistry and dation for all higher level courses. First-year courses introduce
Physics and the NIST Chemistry WebBook (http://webbook. students to the language and discipline of chemistry, and some
nist.gov/). Furthermore, thermodynamic quantities like ¢rH° concepts are not touched on again in the entire undergraduate
are always molar quantities and have the units kJ mol−1, as rec- curriculum. Indeed, many Ph.D. comprehensive questions fall
ommended by IUPAC. Exclusive use of IUPAC-recommended back to ideas learned in first year. This book was prepared with
xx P reface
the full undergraduate curriculum in mind. If you are a student, “Fluoride and Teeth” (Chapter 16), and “Rechargeable Bat-
we hope that the Canadian edition of Chemistry: A Molecular tery Recycling” (Chapter 18). We also added many new end-of
Approach helps you succeed in chemistry. We encourage you chapter problems throughout the book, which gives instructors
to make use of all of the features in this book that are designed and students more opportunities to engage with chemistry con-
to help you learn. If you are a professor, it is our hope that tent and practise problem solving.
this textbook provides you with the strong content you need to
teach first-year chemistry in a way that is true to our discipline. Acknowledgements
Third Canadian Edition During the development of this book, we obtained many help-
ful suggestions and comments from colleagues from across the
For the third Canadian edition, we had two primary goals. Our
country.
first goal was to make focused improvements and write addi-
tional content in selected areas. Some of these are described
below. Editorial Advisory Board
In Chapter 7, we have clarified the language and added We would like to thank the following professors for contribut-
a brief discussion of what is meant by orbital energies. We ing their valuable time to meet with the author and the publish-
improved the discussion of electron configurations of transi- ing team over the course of this project to provide a meaningful
tion metals—a topic that many students find confusing. We also perspective on the most important challenges they face in
added a whole new section showing the application of the teaching general chemistry and for providing insight and feed-
Schrödinger equation to a quantum mechanical system—“the back on the third Canadian edition and MasteringChemistry
particle in a one-dimensional box.” Our aim is to demystify course:
wave functions and quantum numbers. We do this by showing Louise Dawe, Wilfrid Laurier University
that wave functions are nothing more than mathematical equa- Phil Dutton, University of Windsor
tions representing electrons in an atom. Furthermore, applying
Andrew Vreugdenhil, Trent University
the Schrödinger equation to a quantum mechanical system with
James Xidos, University of Manitoba
boundary conditions (i.e., a particle in a box or an electron in an
atom) gives rise to quantum numbers. We also thank the following reviewers who offered feedback
In Chapter 9, we added a brief discussion of homolytic ver- on the previous edition of this textbook:
sus heterolytic bond dissociations. In Chapter 10, we expanded
Francois Caron, Laurentian University
coverage of p–n junctions in diodes and show how these are
applied in light emitting diodes (LEDs) and photovoltaic cells. Linda Davis, McMaster University
We also address the issue of hybridization of terminal atoms Violeta Iosub, University of Calgary
in bonding descriptions. From a shape and structure point of Lori Jones, University of Guelph
view, when a molecule has a terminal atom with lone pairs of Stephen Kariuki, Nipissing University
electrons, it is not necessary to assign hybrid orbitals to those Jan Matejovic, University of Ontario Institute of Technology
lone pairs. However, hybridization of terminal atoms is com- Andrew Mosi, Langara College
monly taught, especially in organic chemistry courses, where Brad Pavelich, Medicine Hat College
reactions result in a bond to the terminal atom. Our continued Jason Pearson, University of Prince Edward Island
priority is to show how chemists use different bonding models
for different purposes. As well, we added stick-like drawings We acknowledge Prof. Dietmar Kennepohl (Athabasca
to show the shapes of molecules—drawings that students can University) and Dr. Nicole Sandblom (University of Calgary),
mimic—along with artistic three-dimensional renderings that Dr. Neil Anderson (Onyx Pharmaceuticals), Dr. Rebecca
students will not be able to reproduce easily. Goyan (Simon Fraser University), Drs. Barry Power, Chris Flinn,
Worked examples are one of the most important and well- Karen Hattenhauer, Mike Katz, Ray Poirier, Peter Warburton,
used features in this textbook. To continue this strength, we and Chris Kozak (Memorial University), Mr. Nicholas Ryan
have added some new worked examples, for example on reac- (Memorial University), and Drs. Lucio Gelmini and Robert
tion mechanisms in Chapter 13. Hilts (MacEwan University) for helpful discussions and their
Finally, we reorganized Chapter 17 slightly by moving the insightful comments.
discussion of the third law of thermodynamics earlier in the Dr. Ian Hunt of the University of Calgary worked with us
chapter with the rest of the quantitative discussion of entropy. in the early development of the organic chemistry chapters. He
We also introduced a new section, including worked examples, provided sage advice on the organization of these chapters and
on making nonspontaneous processes spontaneous by coupling made numerous suggestions on how to present organic chemis-
with exergonic reactions. try in a way that is both rigorous and accessible to the first-year
Our second goal was to update and “evergreen” the book. student.
To do this, we replaced or updated “Chemistry in Your Day” Professor François Caron of Laurentian University pro-
boxes to make them more interesting and relevant to students vided expert advice on revisions to Chapter 19, improving the
and thereby enhance learning. New boxes include “Stack presentation of nuclear reaction energetics so that it is consis-
Sampling” (Chapter 5), “Weak Acids in Wine” (Chapter 15), tent with the field of nuclear chemistry.
P reface xxi
We would like to thank our wives, Lisa and Tanya, for Senior Marketing Manager; Kamilah Reid-Burrell, Content
their encouragement and their continuing patience during all Manager; Martina van de Velde, Content Developer; Jessica
the evenings and weekends we spent working on this book Misfud, Project Manager; Leanne Rancourt, Production Editor
when we could have been with our families. and Proofreader; Susan Broadhurst, Copyeditor; and Anthony
Finally, we would also like to acknowledge the assistance Leung, Senior Designer.
of the many members of the team at Pearson Canada who
were involved throughout the writing and production process: Travis D. Fridgen
Cathleen Sullivan, Executive Acquisitions Editor; Kim Teska, Lawton E. Shaw
Relevant examples and
clear language
C hemistry is relevant to every process occurring around you, at every second. The authors
help you understand this connection by weaving specific, vivid examples throughout the
text that tell the story of chemistry. Every chapter begins with a brief story that illustrates how
chemistry is relevant to all people, at every moment.
xxii
Connect Chemistry to
YOUR WORLD
Student Interest
Throughout the narrative and in special boxed
features, interesting descriptions of chemistry in
the modern world demonstrate its importance.
xxiii
Pioneering artwork makes
Concepts Clear
The goal is for you to connect what you see and experience (the macroscopic world) with the mol-
ecules responsible for that world, and with the way chemists represent those molecules. After all,
this is what chemistry is all about.
Symbolic representation
Molecular image
Macroscopic image
Annotations
tell the story of the
image concisely.
Molecular image
Macroscopic image
xxiv
Multipart Images
Multipart images make connections among graphical
representations, molecular processes, and the macroscopic world.
Symbolic representation
Macroscopic image
Molecular image
Graphical representation
xxv
Consistent strategies help you
Solve Problems
Two-Column Example
A consistent approach to problem solving is used throughout the book.
xxvi
Three-Column Example
Problem-Solving Procedure Boxes for important categories of problems enable
you to see how the same reasoning applies to different problems.
xxvii
End-of-Chapter
Material AIDS Study and Test Prep
End-of-Chapter Review Section
The end-of-chapter review section helps
you study the chapter’s concepts and skills
in a systematic way that is ideal for test
preparation.
xxviii
End-of-Chapter Review Exercises
Answers to odd-numbered questions are in
Appendix III.
xxix
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a water-closet; by some horrid drain; by proximity to a pig-sty; by an
overflowing privy, especially if vegetable matter be rotting at the
same time in it; by bad ventilation, or by contagion. Diphtheria may
generally be traced either to the one or to the other of the above
causes; therefore let me urgently entreat you to look well into all
these matters, and thus to stay the pestilence! Diphtheria might long
remain in a neighborhood if active measures be not used to
exterminate it.
210. Have the goodness to describe the symptoms of Measles?
Measles commences with symptoms of a common cold; the patient
is at first chilly, then hot and feverish; he has a running at the nose,
sneezing, watering and redness of the eyes, headache, drowsiness, a
hoarse and peculiar ringing cough, which nurses call “measle-
cough,” and difficulty of breathing. These symptoms usually last
three days before the eruption appears; on the fourth it (the
eruption) generally makes its appearance, and continues for four
days and then disappears, lasting altogether, from the
commencement of the symptoms of cold to the decline of the
eruption, seven days. It is important to bear in mind that the
eruption consists of crescent-shaped—half-moon-shaped—patches;
that they usually appear first about the face and the neck, in which
places they are the best marked; then on the body and on the arms;
and, lastly, on the legs, and that they are slightly raised above the
surface of the skin. The face is swollen, more especially the eyelids,
which are sometimes for a few days closed.
Well, then, remember, the running at the nose, the sneezing, the
peculiar hoarse cough, and the half-moon-shaped patches, are the
leading features of the disease, and point out for a certainty that it is
measles.
211. What constitutes the principal danger in Measles?
The affection of the chest. The mucous or lining membrane of the
bronchial tubes is always more or less inflamed, and the lungs
themselves are sometimes affected.
212. Do you recommend “surfeit water” and saffron tea to throw
out the eruption in Measles?
Certainly not. The only way to throw out the eruption, as it is
called, is to keep the body comfortably warm, and to give the
beverages ordered by the medical man, with the chill off. “Surfeit
water,” saffron tea, and remedies of that class, are hot and
stimulating. The only effect they can have, will be to increase the
fever and the inflammation—to add fuel to the fire.
213. What is the treatment of Measles?
What to do.—The child ought to be confined both to his room and
to his bed, the room being kept comfortably warm; therefore, if it be
winter time, there should be a small fire in the grate; in the summer
time, a fire would be improper. The child must not be exposed to
draughts; notwithstanding, from time to time, the door ought to be
left a little ajar in order to change the air of the apartment; for proper
ventilation, let the disease be what it may, is absolutely necessary.
Let the child, for the first few days, be kept on a low diet, such as
on milk and water, arrow-root, bread and butter, etc.
If the attack be mild, that is to say, if the breathing be not much
affected (for in measles it always is more or less affected), and if
there be not much wheezing, the acidulated infusion of roses’
mixture[228] will be all that is necessary.
But suppose that the breathing is short, and that there is a great
wheezing, then, instead of giving him the mixture just advised, give
him a teaspoonful of a mixture composed of ipecacuanha wine,
syrup, and water,[229] every four hours. And if, on the following day,
the breathing and the wheezing be not relieved, in addition to the
ipecacuanha mixture, apply a tela vesicatoria, as advised under the
head of inflammation of the lungs.
When the child is convalescing, batter puddings, rice, and sago
puddings, in addition to the milk, bread and butter, etc., should be
given; and, a few days later, chicken, mutton-chops, etc.
The child ought not, even in a mild case of measles, and in
favorable weather, to be allowed to leave the house under a fortnight,
or it might bring on an attack of bronchitis.
What NOT to do.—Do not give either “surfeit water” or wine. Do not
apply leeches to the chest. Do not expose the child to the cold air. Do
not keep the bedroom very hot, but comfortably warm. Do not let the
child leave the house, even under favorable circumstances, under a
fortnight. Do not, while the eruption is out, give aperients. Do not,
“to ease the cough,” administer either emetic tartar or paregoric—the
former drug is awfully depressing; the latter will stop the cough, and
will thus prevent the expulsion of the phlegm.
214. What is the difference between Scarlatina and Scarlet Fever?
They are, indeed, one and the same disease, scarlatina being the
Latin for scarlet fever. But, in a popular sense, when the disease is
mild, it is usually called scarlatina. The latter term does not sound so
formidable to the ears either of patients or of parents.
215. Will you describe the symptoms of Scarlet Fever?
The patient is generally chilly, languid, drowsy, feverish, and
poorly for two days before the eruption appears. At the end of the
second day, the characteristic, bright scarlet efflorescence, somewhat
similar to the color of a boiled lobster, usually first shows itself. The
scarlet appearance is not confined to the skin; but the tongue, the
throat, and the whites of the eyes put on the same appearance; with
this only difference, that on the tongue and on the throat the scarlet
is much darker; and, as Dr. Elliotson accurately describes it,—“the
tongue looks as if it had been slightly sprinkled with Cayenne
pepper.” The eruption usually declines on the fifth, and is generally
indistinct on the sixth day; on the seventh it has completely faded
away. There is usually, after the first few days, great itching on the
surface of the body. The skin, at the end of the week, begins to peel
and to dust off, making it look as though meal had been sprinkled
upon it.
There are three forms of scarlet fever,—the one where the throat is
little, if at all affected, and this is a mild form of the disease; the
second, which is generally, especially at night, attended with
delirium, where the throat is much affected, being often greatly
inflamed and ulcerated; and the third (which is, except in certain
unhealthy districts, comparatively rare, and which is VERY
dangerous), the malignant form.
216. Would it be well to give a little cooling, opening physic as
soon as a child begins to sicken for Scarlet Fever?
On no account whatever. Aperient medicines are, in my opinion,
highly improper and dangerous both before and during the period of
the eruption. It is my firm conviction that the administration of
opening medicine, at such times, is one of the principal causes of
scarlet fever being so frequently fatal. This is, of course, more
applicable to the poor, and to those who are unable to procure a
skillful medical man.
217. What constitutes the principal danger in Scarlet Fever?
The affection of the throat, the administration of opening medicine
during the first ten days, and a peculiar disease of the kidneys ending
in anasarca (dropsy), on which account, the medical man ought,
when practicable, to be sent for at the onset, that no time may be lost
in applying proper remedies.
218. How would you distinguish between Scarlet Fever and
Measles?
Measles commences with symptoms of a common cold; scarlet
fever does not. Measles has a peculiar hoarse cough; scarlet fever has
not. The eruption of measles is in patches of a half-moon shape, and
is slightly raised above the skin; the eruption of scarlet fever is not
raised above the skin at all, and is one continued mass. The color of
the eruption is much more vivid in scarlet fever than in measles. The
chest is the part principally affected in measles, and the throat in
scarlet fever.
There is an excellent method of determining, for a certainty,
whether the eruption be that of scarlatina or otherwise. I myself
have, in several instances, ascertained the truth of it: “For several
years M. Bouchut has remarked in the eruption of scarlatina a
curious phenomenon, which serves to distinguish this eruption from
that of measles, erythema, erysipelas, etc., a phenomenon essentially
vital, and which is connected with the excessive contractability of the
capillaries. The phenomenon in question is a white line, which can
be produced at pleasure by drawing the back of the nail along the
skin where the eruption is situated. On drawing the nail, or the
extremity of a hard body (such as a pen-holder), along the eruption,
the skin is observed to grow pale, and to present a white trace, which
remains for one or two minutes, or longer, and then disappears. In
this way the diagnosis of the disease may be very distinctly written
on the skin; the word ‘Scarlatina’ disappears as the eruption regains
its uniform tint.”[230]
219. Is it of so much importance, then, to distinguish between
Scarlet Fever and Measles?
It is of great importance, as in measles the patient ought to be kept
moderately warm, and the drinks should be given with the chill off;
while in scarlet fever the patient ought to be kept cool—indeed, for
the first few days, cold; and the beverages, such as spring water, toast
and water, etc., should be administered quite cold.
220. What is the treatment of Scarlet Fever?[231]
What to do.—Pray pay particular attention to my rules, and carry
out my directions to the very letter—as I can then promise you that if
the scarlet fever be not malignant, the plan I am about to
recommend will, with God’s blessing, be generally successful.
What is the first thing to be done? Send the child to bed; throw
open the windows, be it winter or summer, and have a thorough
ventilation; for the bedroom must be kept cool, I may say cold. Do
not be afraid of fresh air, for fresh air, for the first few days, is
essential to recovery. Fresh air, and plenty of it, in scarlet fever, is
the best doctor a child can have: let these words be written legibly on
your mind.[232]
Take down the curtains of the bed; remove the valances. If it be
summer time, let the child be only covered with a sheet: if it be
winter time, in addition to the sheet, he should have one blanket over
him.
Now for the throat.—The best external application is a barm and
oatmeal poultice. How ought it to be made, and how applied? Put
half a teacupful of barm into a saucepan, put it on the fire to boil; as
soon as it boils take it off the fire, and stir oatmeal into it, until it is of
the consistence of a nice soft poultice; then place it on a rag, and
apply it to the throat; carefully fasten it on with bandage, two or
three turns of the bandage going round the throat, and two or three
over the crown of the head, so as nicely to apply the poultice where it
is wanted—that is to say, to cover the tonsils. Tack the bandage: do
not pin it. Let the poultice be changed three times a day. The best
medicine is the acidulated infusion of roses, sweetened with syrup.
[233]
It is grateful and refreshing, it is pleasant to take, it abates fever
and thirst, it cleans the throat and tongue of mucus, and is peculiarly
efficacious in scarlet fever; as soon as the fever is abated it gives an
appetite. My belief is that the sulphuric acid in the mixture is a
specific in scarlet fever, as much as quinine is in ague, and sulphur in
itch. I have reason to say so, for, in numerous cases, I have seen its
immense value.
Now, with regard to food.—If the child be at the breast, keep him
entirely to it. If he be weaned, and under two years old, give him milk
and water, and cold water to drink. If he be older, give him toast and
water, and plain water from the pump, as much as he chooses; let it
be quite cold—the colder the better. Weak black tea, or thin gruel,
may be given, but not caring, unless he be an infant at the breast, if
he take nothing but cold water. If the child be two years old and
upwards, roasted apples with sugar, and grapes will be very
refreshing, and will tend to cleanse both the mouth and the throat.
Avoid broths and stimulants of every kind.
When the appetite returns, you may consider the patient to be
safe. The diet ought now to be gradually improved. Bread and butter,
milk and water, and arrow-root made with equal parts of new milk
and water, should for the first two or three days be given. Then a
light batter or rice pudding may be added, and in a few days
afterward, either a little chicken or a mutton-chop.
The essential remedies, then, in scarlet fever, are, for the first few
days—(1) plenty of fresh air and ventilation, (2) plenty of cold water
to drink, (3) barm poultices to the throat, and (4) the acidulated
infusion of roses’ mixture as a medicine.
Now, then, comes very important advice. After the first few days,
probably five or six, sometimes as early as the fourth day, watch
carefully and warily, and note the time, the skin will suddenly
become cool, the child will say that he feels chilly; then is the time
you must now change your tactics—instantly close the windows, and
put extra clothing, a blanket or two, on his bed. A flannel night-gown
should, until the dead skin has peeled off, be now worn next to the
skin, when the flannel night-gown should be discontinued. The
patient ought ever after to wear, in the daytime, a flannel waistcoat.
[234]
His drinks must now be given with the chill off; he ought to have
a warm cup of tea, and gradually his diet should, as I have previously
recommended be improved.
There is one important caution I wish to impress upon you,—do
not give opening medicine during the time the eruption is out. In all
probability the bowels will be opened: if so, all well and good; but do
not, on any account, for the first ten days, use artificial means to
open them. It is my firm conviction that the administration of
purgatives in scarlet fever is a fruitful source of dropsy, of disease,
and death. When we take into consideration the sympathy there is
between the skin and the mucous membrane, I think that we should
pause before giving irritating medicines, such as purgatives. The
irritation of aperients on the mucous membrane may cause the
poison of the skin disease (for scarlet fever is a blood poison) to be
driven internally to the kidneys, to the throat, to the pericardium
(bag of the heart), or to the brain. You may say, Do you not purge if
the bowels be not open for a week? I say emphatically, No!
I consider my great success in the treatment of scarlet fever to be
partly owing to my avoidance of aperients during the first ten days of
the child’s illness.
If the bowels, after the ten days, are not properly opened, a dose or
two of the following mixture should be given:
Take of—Simple Syrup, three drachms;
Essence of Senna, nine drachms:
Make a Liniment.
Let him wear a broad band of new flannel, which should extend
round from his chest to his back, and which ought to be changed
every night and morning, in order that it may be dried before putting
on again. To keep it in its place it should be fastened by means of
tapes and with shoulder-straps.
The diet ought now to be improved—he should gradually return to
his usual food; and, weather permitting, should almost live in the
open air—fresh air being, in such a case, one of the finest medicines.
In the third stage, that is to say, when the complaint has lasted a
month, if by that time the child is not well, there is nothing like
change of air to a high, dry, healthy, country place. Continue the
nitric acid mixture, and either the embrocation or the liniment to the
back and the chest, and let him continue to almost live in the open
air, and be sure that he does not discontinue wearing the flannel
until he be quite cured, and then let it be left off by degrees.
If the hooping-cough have caused debility, give him cod-liver oil, a
teaspoonful twice or three times a day, giving it him on a full
stomach after his meals.
But, remember, after the first three or four weeks, change of air,
and plenty of it, is for hooping-cough the grand remedy.
What NOT to do.—Do not apply leeches to the chest, for I would
rather put blood into a child laboring under hooping-cough than take
it out of him—hooping-cough is quite weakening enough to the
system of itself without robbing him of his life’s blood; do not, on any
account whatever, administer either emetic tartar or antimonial
wine; do not give either paregoric or syrup of white poppies; do not
drug him either with calomel or with gray powder; do not dose him
with quack medicine; do not give him stimulants, but rather give him
plenty of nourishment, such as milk and farinaceous food, but no
stimulants; do not be afraid, after the first week or two, of his having
fresh air, and plenty of it—for fresh, pure air is the grand remedy,
after all that can be said and done, in hooping-cough. Although
occasionally we find that if the child be laboring under hooping-
cough and is breathing a pure country air, and is not getting well so
rapidly as we could wish, change of air to a smoky, gas-laden town
will sometimes quickly effect a cure; indeed, some persons go so far
as to say that the best remedy for an obstinate case of hooping-cough
is for the child to live the great part of every day in gas-works!
231. What is to be done during a paroxysm of Hooping-cough?
If the child be old enough, let him stand up; but if he be either too
young or too feeble, raise his head, and bend his body a little
forward; then support his back with one hand, and the forehead with
the other. Let the mucus, the moment it is within reach, be wiped
with a soft handkerchief out of his mouth.
232. In an obstinate case of Hooping-cough, what is the best
remedy?
Change of air, provided there be no active inflammation, to any
healthy spot. A farm-house, in a high, dry, and salubrious
neighborhood, is as good a place as can be chosen. If, in a short time,
he be not quite well, take him to the sea-side: the sea breezes will
often, as if by magic, drive away the disease.
233. Suppose my child should have a shivering fit, is it to be
looked upon as an important symptom?
Certainly. Nearly all serious illnesses commence with a shivering
fit: severe colds, influenza, inflammations of different organs, scarlet
fever, measles, small-pox, and very many other diseases, begin in
this way. If, therefore, your child should ever have a shivering fit,
instantly send for a medical man, as delay might be dangerous. A few
hours of judicious treatment, at the commencement of an illness, is
frequently of more avail than days and weeks, nay months, of
treatment, when disease has gained a firm footing. A serious disease
often steals on insidiously, and we have, perhaps, only the shivering
fit, which might be but a slight one, to tell us of its approach.
A trifling ailment, too, by neglecting the premonitory symptom,
which, at first, might only be indicated by a slight shivering fit, will
sometimes become a mortal disorder:
“The little rift within the lute,
That by-and-by will make the music mute,
And ever widening slowly silence all.”[242]