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(BQ) Part 1 book Chemistry has contents: Chemical foundations; atoms, molecules, and ions, stoichiometry; types of chemical reactions and solution stoichiometry; gases, thermochemistry; atomic structure and periodicity; covalent bonding orbitals; bonding general concepts; liquids and solids, properties of solutions.

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Chemistry Seventh Edition

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Senior Project Editor: Cathy Labresh Brooks

Editorial Assistant: Susan Miscio

Senior Art & Design Coordinator: Jill Haber

Composition Buyer: Chuck Dutton

Manufacturing Coordinator: Renee Ostrowski

Senior Marketing Manager: Katherine Greig

Marketing Assistant: Naveen Hariprasad

Cover image: Masaaki Kazama/Photonica

Photo credits: Page A39.

Copyright © 2007 by Houghton Mifflin Company All rights reserved.

No part of this work may be reproduced or transmitted in any form or by any means, tronic or mechanical, including photocopying and recording, or by any information storage

elec-or retrieval system without the prielec-or written permission of Houghton Mifflin Company unless such copying is expressly permitted by federal copyright law Address inquiries to College Permissions, Houghton Mifflin Company, 222 Berkeley Street, Boston, MA 02116-3764.

Printed in the U.S.A.

Library of Congress Catalog Card Number: 2005929890

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Molecules, or Making Elephants Fly 87

3.5 Percent Composition of Compounds 89

3.6 Determining the Formula of a Compound 91

3.7 Chemical Equations 96

3.8 Balancing Chemical Equations 98

3.9 Stoichiometric Calculations: Amounts of Reactants andProducts 102

Octane 103

3.10 Calculations Involving a Limiting Reactant 106For Review 113 • Key Terms 113 • Questions andExercises 115

Solution Stoichiometry 126

4.1 Water, the Common Solvent 127

4.2 The Nature of Aqueous Solutions: Strong and WeakElectrolytes 129

Solutions 132

4.3 The Composition of Solutions 133

4.4 Types of Chemical Reactions 140

4.5 Precipitation Reactions 140

4.6 Describing Reactions in Solution 145

4.7 Stoichiometry of Precipitation Reactions 147

4.8 Acid–Base Reactions 149

4.9 Oxidation–Reduction Reactions 154

Pollution 156

Oxidation? 160

4.10 Balancing Oxidation–Reduction Equations 162

For Review 168 • Key Terms 168 • Questions andExercises 170

1.2 The Scientific Method 5

2.1 The Early History of Chemistry 39

2.2 Fundamental Chemical Laws 41

2.3 Dalton’s Atomic Theory 43

2.4 Early Experiments to Characterize the Atom 45

2.5 The Modern View of Atomic Structure:

An Introduction 49

2.6 Molecules and Ions 52

2.7 An Introduction to the Periodic Table 55

2.8 Naming Simple Compounds 57

For Review 67 • Key Terms 67 • Question and

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5.1 Pressure 179

5.2 The Gas Laws of Boyle, Charles, and Avogadro 181

5.3 The Ideal Gas Law 186

5.4 Gas Stoichiometry 190

5.5 Dalton’s Law of Partial Pressures 194

5.6 The Kinetic Molecular Theory of Gases 199

5.7 Effusion and Diffusion 206

5.8 Real Gases 208

5.9 Characteristics of Several Real Gases 210

5.10 Chemistry in the Atmosphere 211

For Review 215 • Key Terms 215 • Questions and

Exercises 217

6.1 The Nature of Energy 229

6.2 Enthalpy and Calorimetry 235

6.3 Hess’s Law 242

6.4 Standard Enthalpies of Formation 246

6.5 Present Sources of Energy 252

6.6 New Energy Sources 256

For Review 264 • Key Terms 264 • Questions and

Exercises 265

7.1 Electromagnetic Radiation 275

7.2 The Nature of Matter 277

the Dark 280

7.3 The Atomic Spectrum of Hydrogen 284

7.4 The Bohr Model 285

7.5 The Quantum Mechanical Model of the Atom 290

7.6 Quantum Numbers 293

7.7 Orbital Shapes and Energies 295

7.8 Electron Spin and the Pauli Principle 296

7.9 Polyelectronic Atoms 298

7.10 The History of the Periodic Table 299

7.11 The Aufbau Principle and the Periodic Table 302

7.12 Periodic Trends in Atomic Properties 309

7.13 The Properties of a Group: The Alkali Metals 314

Thing Can Kill You 317For Review 318 • Key Terms 318 • Questions andExercises 320

8.1 Types of Chemical Bonds 330

8.2 Electronegativity 333

8.3 Bond Polarity and Dipole Moments 335

8.4 Ions: Electron Configurations and Sizes 338

8.5 Energy Effects in Binary Ionic Compounds 342

8.6 Partial Ionic Character of Covalent Bonds 346

8.7 The Covalent Chemical Bond: A Model 347

8.8 Covalent Bond Energies and Chemical Reactions 350

8.9 The Localized Electron Bonding Model 353

8.10 Lewis Structures 354

8.11 Exceptions to the Octet Rule 358

8.12 Resonance 362

8.13 Molecular Structure: The VSEPR Model 367

Communication: Semiochemicals 378For Review 380 • Key Terms 380 • Questions andExercises 382

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9.1 Hybridization and the Localized Electron Model 391

9.2 The Molecular Orbital Model 403

9.3 Bonding in Homonuclear Diatomic Molecules 406

9.4 Bonding in Heteronuclear Diatomic Molecules 412

9.5 Combining the Localized Electron and Molecular

Orbital Models 413

For Review 416 • Key Terms 416 • Questions and

Exercises 417

10.1 Intermolecular Forces 426

10.2 The Liquid State 429

10.3 An Introduction to Structures and Types of

Solids 430

10.4 Structure and Bonding in Metals 436

10.5 Carbon and Silicon: Network Atomic Solids 444

Fooling Mother Nature 470

For Review 472 • Key Terms 472 • Questions and

Exercises 474

11.1 Solution Composition 485

11.2 The Energies of Solution Formation 488

11.3 Factors Affecting Solubility 492

11.4 The Vapor Pressures of Solutions 497

11.5 Boiling-Point Elevation and Freezing-Point

Depression 504

11.6 Osmotic Pressure 508

11.7 Colligative Properties of Electrolyte Solutions 512

Water 514

11.8 Colloids 514

For Review 516 • Key Terms 516 • Questions andExercises 518

12.1 Reaction Rates 527

12.2 Rate Laws: An Introduction 532

12.3 Determining the Form of the Rate Law 534

12.4 The Integrated Rate Law 538

12.5 Rate Laws: A Summary 548

12.6 Reaction Mechanisms 549

12.7 A Model for Chemical Kinetics 552

12.8 Catalysis 557

For Review 564 • Key Terms 564 • Questions andExercises 566

13.1 The Equilibrium Condition 579

13.2 The Equilibrium Constant 582

13.3 Equilibrium Expressions Involving Pressures 586

13.4 Heterogeneous Equilibria 588

13.5 Applications of the Equilibrium Constant 591

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14.1 The Nature of Acids and Bases 623

14.8 Acid–Base Properties of Salts 655

14.9 The Effect of Structure on Acid–Base

Properties 661

15.7 Precipitation and Qualitative Analysis 724

15.8 Equilibria Involving Complex Ions 731For Review 736 • Key Terms 736 • Questions andExercises 739

Energy 748

16.1 Spontaneous Processes and Entropy 749

16.2 Entropy and the Second Law of Thermodynamics 755

16.3 The Effect of Temperature on Spontaneity 756

16.4 Free Energy 759

16.5 Entropy Changes in Chemical Reactions 762

16.6 Free Energy and Chemical Reactions 766

16.7 The Dependence of Free Energy on Pressure 770

16.8 Free Energy and Equilibrium 774

16.9 Free Energy and Work 778For Review 780 • Key Terms 780 • Questions andExercises 782

17.1 Galvanic Cells 791

17.2 Standard Reduction Potentials 794

17.3 Cell Potential, Electrical Work, and Free Energy 800

17.4 Dependence of Cell Potential on Concentration 803

17.5 Batteries 808

from Heat 810

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17.8 Commercial Electrolytic Processes 821

For Review 826 • Key Terms 826 • Questions and

Exercises 829

18.1 Nuclear Stability and Radioactive Decay 841

18.2 The Kinetics of Radioactive Decay 846

18.3 Nuclear Transformations 849

18.4 Detection and Uses of Radioactivity 852

18.5 Thermodynamic Stability of the Nucleus 856

18.6 Nuclear Fission and Nuclear Fusion 859

19.1 A Survey of the Representative Elements 875

19.2 The Group 1A Elements 880

19.3 Hydrogen 883

19.4 The Group 2A Elements 885

19.5 The Group 3A Elements 888

19.6 The Group 4A Elements 890

For Review 894 • Key Terms 894 • Questions and

Exercises 895

5A Through 8A 900

20.1 The Group 5A Elements 901

20.2 The Chemistry of Nitrogen 903

Propels Whipped Cream and Cars 912

20.3 The Chemistry of Phosphorus 913

Element 914

20.4 The Group 6A Elements 918

20.5 The Chemistry of Oxygen 919

20.6 The Chemistry of Sulfur 920

20.7 The Group 7A Elements 924

20.8 The Group 8A Elements 931

For Review 933 • Key Terms 933 • Questions andExercises 936

Chemistry 942

21.1 The Transition Metals: A Survey 943

21.2 The First-Row Transition Metals 949

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22.6 Natural Polymers 1025

For Review 1040 • Key Terms 1040 • Questions andExercises 1044

Appendix 1 Mathematical Procedures A1

A1.1 Exponential Notation A1

A1.2 Logarithms A4

A1.3 Graphing Functions A6

A1.4 Solving Quadratic Equations A7

A1.5 Uncertainties in Measurements A10

Appendix 2 The Quantitative Kinetic Molecular

Model A13

Appendix 3 Spectral Analysis A16

Appendix 4 Selected Thermodynamic Data A19

Appendix 5 Equilibrium Constants and Reduction

A5.3 Values of Kbfor Some Common Weak Bases A23

A5.4 KspValues at 25C for Common Ionic Solids A24

A5.5 Standard Reduction Potentials at 25C (298K) forMany Common Half-Reactions A25

Appendix 6 SI Units and Conversion Factors A26

Glossary A27

Photo Credits A39

Answers to Selected Exercises A41

Index A70

21.5 Bonding in Complex Ions: The Localized Electron

21.6 The Crystal Field Model 967

to Gems 970

21.7 The Biologic Importance of Coordination

Complexes 973

21.8 Metallurgy and Iron and Steel Production 978

For Review 987 • Key Terms 987 • Questions and

Exercises 989

22.1 Alkanes: Saturated Hydrocarbons 997

22.2 Alkenes and Alkynes 1005

22.3 Aromatic Hydrocarbons 1008

22.4 Hydrocarbon Derivatives 1010

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With this edition of Chemistry, students and instructors

alike will experience a truly integrated learning program The

textbook’s strong emphasis on conceptual learning and

prob-lem solving is extended through the numerous online media

as-signments and activities It was our mission to create a media

program that embodies the spirit of the textbook so that, when

instructors and students look online for either study aids or

on-line homework, that each resource supports the goals of the

textbook—a strong emphasis on models, real-world

applica-tions, and visual learning

We have gone over every page in the sixth edition

thor-oughly, fine-tuning in some cases and rewriting in others In

doing so, we have incorporated numerous constructive

sugges-tions from instructors who used the previous edition Based on

this feedback new content has been added, such as the

treat-ment of real gases in Chapter 5, which has been expanded to

include a discussion of specific gases, and also coverage of

pho-toelectric effect has been added to Chapter 7 In addition, the

Sample Exercises in Chapter 2 have been revised to cover the

naming of compounds given the formula and the opposite

process of writing the formula from the name To help students

review key concepts, the For Review section of each chapter

has been reorganized to provide an easy-to-read bulleted

sum-mary; this section includes new review questions The art

pro-gram has been enhanced to include electrostatic potential maps

to show a more accurate distribution of charge in molecules

In the media program instructors will find a variety of

re-sources to assign additional practice, study, and quiz

mater-ial ChemWork interactive assignments, end-of-chapter online

homework, HM Testing, and classroom response system

ap-plications allow you to assess students in multiple ways The

Online Study Center promotes self-study with animations,

video demonstrations, and practice exercises

Important Features of Chemistry

and exercises aimed at overcoming common

misconcep-tions It has become increasingly clear from our own

teach-ing experience that students often struggle with chemistry

because they misunderstand many of the fundamental

con-cepts In this text, we have gone to great lengths to

pro-vide illustrations and explanations aimed at giving students

more accurate pictures of the fundamental ideas of

chem-istry In particular, we have attempted to represent the

microscopic world of chemistry so that students have a

pic-ture in their minds of “what the atoms and molecules are

doing.” The art program along with animations emphasizethis goal Also, we have placed a larger emphasis on thequalitative understanding of concepts before quantitativeproblems are considered Because using an algorithm tocorrectly solve a problem often masks misunderstanding—students assume they understand the material because theygot the right “answer”—it is important to probe theirunderstanding in other ways In this vein the text includes

a number of Active Learning Questions (previously calledIn-Class Discussion Questions) at the end of each chapterthat are intended for group discussion It is our experiencethat students often learn the most when they teach eachother Students are forced to recognize their own lack ofconceptual understanding when they try and fail to explain

a concept to a colleague

With a strong problem-solving orientation, this text talks to

the student about how to approach and solve chemical lems We have made a strong pitch to students for using athoughtful and logical approach rather than simply memo-rizing procedures In particular, an innovative method isgiven for dealing with acid–base equilibria, the material thetypical student finds most difficult and frustrating The key

prob-to this approach involves first deciding what species are sent in solution, then thinking about the chemical properties

pre-of these species This method provides a general frameworkfor approaching all types of solution equilibria

The text contains almost 300 sample exercises, with many

more examples given in the discussions leading to sampleexercises or used to illustrate general strategies When a spe-cific strategy is presented, it is summarized, and the sampleexercise that follows it reinforces the step-by-step attack onthe problem In general, in approaching problem solving weemphasize understanding rather than an algorithm-basedapproach

We have presented a thorough treatment of reactions that

occur in solution, including acid–base reactions This rial appears in Chapter 4, directly after the chapter on chem-ical stoichiometry, to emphasize the connection betweensolution reactions and chemical reactions in general Theearly presentation of this material provides an opportunity

mate-to cover some interesting descriptive chemistry and also ports the lab, which typically involves a great deal of aque-ous chemistry Chapter 4 also includes oxidation–reductionreactions, because a large number of interesting and impor-tant chemical reactions involve redox processes However,coverage of oxidation–reduction is optional at this point anddepends on the needs of a specific course

sup-To the Professor

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Descriptive chemistry and chemical principles are

thor-oughly integrated in this text Chemical models may appear

sterile and confusing without the observations that

stimu-lated their invention On the other hand, facts without

orga-nizing principles may seem overwhelming A combination

of observations and models can make chemistry both

inter-esting and understandable In addition, in those chapters that

deal with the chemistry of the elements systematically, we

have made a continuous effort to show how properties and

models correlate Descriptive chemistry is presented in a

va-riety of ways—as applications of the principles in separate

sections, in Sample Exercises and exercise sets, in

pho-tographs, and in Chemical Impact features

Throughout the book a strong emphasis on models prevails.

Coverage includes how they are constructed, how they are

tested, and what we learn when they inevitably fail

Mod-els are developed naturally, with pertinent observations

always presented first to show why a particular model was

invented

Everyday-life applications of chemistry that should be of

interest to students taking general chemistry appear

throughout the text For example, the Chemical Impact

“Pearly Whites” illustrates the procedures for keeping teeth

white, and “Thin is In” discusses the new technology being

used to produce plasma flat-panel displays Many industrial

applications have also been incorporated into the text

A double-helix icon in the Instructor’s Annotated Edition

highlights organic and biological examples of applications

that are integrated throughout the text, in end-of-chapter

problems, in exercises, or in-text discussions or examples

This feature allows instructors to quickly locate material that

will be of particular interest to students in pre-medicine,

biology, or other health-related fields

● Judging from the favorable comments of instructors and

students who have used the sixth edition, the text seemed

to work very well in a variety of courses We were

espe-cially pleased that readability was cited as a key strength

when students were asked to assess the text Thus, although

the text has been fine-tuned in many areas, we have

en-deavored to build on the basic descriptions, strategies,

analogies, and explanations that were successful in the

pre-vious editions

New to the Seventh Edition

The seventh edition of Chemistry incorporates many significant

improvements and is accompanied by new and enhanced

me-dia products and support services

● Electrostatic potential maps have been added to Chapter 8

to show a more accurate distribution of charge in molecules

These maps are based on ab initio molecular modeling

calculations and provide a convenient method for better

student understanding of bond and molecular polarity

● Additional topics have been added to the text, which include

a treatment of real gases in Chapter 5 and coverage ofphotoelectric effect to Chapter 7 In addition, the SampleExercises in Chapter 2 have been revised to cover the nam-ing of compounds given the formula and the oppositeprocess of writing the formula from the name

● The end-of-chapter exercises and problems have beenrevised, providing approximately 20% new problems, in-cluding some that feature molecular art End-of-chapter

problems include: Active Learning Questions to test students’ conceptual grasp of the material; Questions to help review important facts; Exercises that are paired and organized by topic; Additional Exercises, which are not keyed by topic; Challenge Problems, which require students

to combine skills and problems; and Marathon Problems,

which are the most comprehensive and challenging type

of problem New to the seventh edition are Integrative

Problems that require students to understand multiple

concepts across chapters

The For Review section, at the beginning of the

end-of-chapter exercises, has been reorganized to help studentsmore easily identify key concepts and test themselves onthese concepts with review questions

● A large number of new Chemical Impacts have been cluded in the seventh edition to continue the emphasis onup-to-date application of chemistry in the real world Theseessays feature intriguing topics such as “Faux Snow,” and

in-“Closest Packing of M&M’s®.”

● To support the use of active learning in chemical education,

we have created new PowerPoint presentations—Active

Learning PowerPoints with Lecture Outlines These

Power-Point presentations feature in-class discussion questions

called Reacts, chemical demonstrations, animations, and

fig-ures from the text This material is designed to help structors present chemistry using an interactive teachingstyle, which we believe is most effective in promoting stu-

in-dent learning An Active Learning Guide includes the

dis-cussion questions and supporting information in a workbookformat The questions are repeated in the workbook (withspace to record answers) so that students can focus on par-ticipation in class sessions This guide can then be used ef-fectively for independent student review outside of class

● The Online Study Center has been enhanced to include avariety of tools to support visual learning and to give stu-

dents extra practice A For Review section summarizes the

key topics of each chapter and helps students visualize the

concepts with animations and video demonstrations

Visu-alization quiz questions allow students to test their

knowl-edge of the concepts presented through the animations and

video demonstrations ACE practice tests allow students to

practice problems on their own, and get immediate back Additional resources include a molecule library, in-teractive periodic table, and flashcards to help students studykey terms

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feed-To the Professor xi

● A very important feature accompanying the seventh edition

is the online homework in the Eduspace®online learning

tool In addition to new algorithmic end-of-chapter

ques-tions, Eduspace also includes ChemWork™ interactive

on-line homework ChemWork is structured to help students

learn chemistry in a conceptual way and is a series of

text-based assignments The system is modeled on a one-to-one

teacher- student problem session When a student cannot

an-swer a given question, instead of giving him/her the correct

answer, a system of interactive hints is available to help them

think through each problem Often the hints are in the form

of a question on which the student receives feedback Links

to text material are also available for reference to key

con-cepts at points of learning The philosophy behind the

home-work is to help students understand the material so that they

can arrive at the correct answer by their own efforts,

sup-ported by the kind of help an instructor would provide in a

one-to-one tutoring session

Another important feature of this homework system is

that each student, even in a very large course, receives a

unique set of tasks for each homework assignment, which

is accomplished using random number–generation and

sim-ilar versions of algorithmic problems Each student’s work

is assessed by the system, and the score for each task in the

assignment is recorded in the electronic gradebook for

im-mediate access by both student and instructor The system

also encourages increased student responsibility by setting

firm deadlines for assignments From the instructor’s

per-spective, Eduspace encourages student study without the

burden of tracking student efforts through grading Our

ex-perience with a similar system at the University of Illinois

convinces us that this interactive homework represents an

important breakthrough in helping students learn chemistry

Flexibility of Topic Order

The order of topics in the text was chosen because it is

pre-ferred by the majority of instructors However, we consciously

constructed the book so that many other orders are possible

During our tenure at the University of Illinois, for a two-chapter

sequence, we used the chapters in this order: 1–6, 13–15, 7–9,

18, 21, 12, 10, 11, 16, 17, and parts of 22 Sections of

Chap-ters 19, 20, and parts of 22 are used throughout the two

se-mesters as appropriate This order, chosen because of the way

the laboratory is organized, is not necessarily recommended,

but it illustrates the flexibility of order built into the text

Some specific points about topic order:

● About half of chemistry courses present kinetics before

equi-libria; the other half present equilibria first This text is

writ-ten to accommodate either order

● The introductory aspects of thermodynamics are presented

relatively early (in Chapter 6) because of the importance of

energy in various chemical processes and models, but the

more subtle thermodynamic concepts are left until later(Chapter 16) These two chapters may be used together ifdesired

● To make the book more flexible, the derivation of the idealgas law from the kinetic molecular theory and quantitativeanalysis using spectroscopy are presented in the appendixes.Although mainstream general chemistry courses typically donot cover this material, some courses may find it appropriate

By using the optional material in the appendixes and by signing the more difficult end-of-chapter exercises (from theadditional exercises section), an instructor will find the level

as-of the text appropriate for many majors courses or for othercourses requiring a more extensive coverage of these topics

● Because some courses cover bonding using only a Lewisstructure approach, orbitals are not presented in the intro-ductory chapter on bonding (Chapter 8) In Chapter 9 bothhybridization and the molecular orbital model are covered,but either or both of these topics may be omitted if desired

● Chapter 4 can be tailored to fit the specific course involved.Used in its entirety where it stands in the book, it providesinteresting examples of descriptive chemistry and supportsthe laboratory program Material in this chapter can also beskipped entirely or covered at some later point, wheneverappropriate For example, the sections on oxidation andreduction can be taught with electrochemistry Althoughmany instructors prefer early introduction of this concept,these sections can be omitted without complication since thenext few chapters do not depend on this material

Supplements

An extensive teaching and learning package has been designed

to make this book more useful to both instructors and students

Technology: For Instructors

Chemistry is accompanied by a complete suite of teaching and

learning tools, including the customizable media resources low Whether online or via CD, these integrated resources aredesigned to save you time and help make class preparation, pre-sentation, assessment, and course management more efficientand effective

be-● Media Integration Guide for Instructors is your portal to

the digital assets for this text It includes the CDs describedbelow as well as a user name and password to the OnlineTeaching Center, giving you instant access to text-relatedmaterials

HM ClassPrep™ CD includes everything an instructor needs

to develop lectures: Active Learning PowerPoints with

Lec-ture Outlines; virtually all text figures, tables, and photos in

PowerPoint slides and as JPEGs; the Instructor’s Resource

Guide in Word; Word files of the printed Test Bank; and Word

files of the Complete Solutions Manual.

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HM Testing™ (powered by Diploma ®) is Houghton Mifflin’s

new version of HM Testing It significantly improves on

functionality and ease of use by offering instructors all the

tools they will need to create, author, deliver, and customize

multiple types of tests—including authoring and editing

algorithmic questions New content includes 150 new

Con-ceptual Questions, skill-level coding, and preprogrammed,

algorithmic questions HM Testing combines a flexible

test-editing program with a comprehensive gradebook

func-tion for easy administrafunc-tion and tracking It enables

in-structors to administer tests via print, network server, or the

web The HM Testing database contains a wealth of

ques-tions and can produce multiple-choice, true/false,

fill-in-the-blank, and essay tests Questions can be customized

based on the chapter being covered, the question format,

level of difficulty, and specific topics Available on the

HM ClassPrep CD

HM ClassPresent™ 2006: General Chemistry features

new animations and video demonstrations HM

ClassPre-sent provides a library of high-quality, scaleable lab

demon-strations and animations covering core chemistry concepts

arranged by chapter and topic The resources within it can

be browsed by thumbnail and description or searched by

chapter, title, or keyword Instructors can export the

anima-tions and videos into a variety of presentation formats or use

for presentation directly from the CD Full transcripts

ac-company all audio commentary to reinforce visual

presen-tations and to cater to different learning styles

Online Teaching Center includes classroom presentation

and preparation materials Animations; videos; virtually all

figures, tables, and photos from the text are available in

JPEG and PowerPoint format; the Transition Guide from the

sixth to seventh edition; Active Learning PowerPoints with

Lecture Outlines; and classroom response system content

are all available online

Eduspace (powered by Blackboard™), Houghton Mifflin’s

complete course-management solution, features

algorith-mic, end-of-chapter questions along with ChemWork

in-teractive online homework Both types of homework

prob-lems include links to relevant pages from the text These

integrated resources allow students to reference core

con-cepts at the point of learning ChemWork assignments help

students learn the process of thinking like a chemist: as

students work through unique, text-based assignments, a

system of interactive hints is available to help them think

through each problem Eduspace includes all of

Black-board’s powerful features for teaching and learning, and

comes preloaded with course materials including videos

and animations, and a link to SMARTHINKING™ live

online tutoring Customized functions allow instructors to

tailor these materials to their specific needs, select, create

and post homework assignments and tests, communicate

with students in a variety of different ways, track studentprogress, and manage their portfolio of course work in thegradebook To help instructors best utilize the media thataccompanies the textbook, lesson plans have been createdbased on the sections of the book Each section correlates

the relevant ChemWork assignments, Visualization

(ani-mations and videos), and online end-of-chapter questions

Please note: instructors who want their students to use

Eduspace must request a Getting Started Guide for dents which will be bundled free with new copies of the

Stu-text Instructors who adopt Eduspace will receive a

separate Getting Started Guide for Instructors for the

program with a passkey to set up their course.

Classroom Response System (CRS) compatible content on

the Online Teaching Center, HM ClassPrep CD, and in space allows professors to perform “on-the-spot” assess-ments, deliver quick quizzes, gauge students’ understanding

Edu-of a particular question or concept, and take their class ter easily Students get immediate feedback on how well theyknow the content and where they need to improve Two sets

ros-of questions are available in PowerPoint slides: one based

on Test Bank content and the other with unique, conceptual

questions Both question types are correlated to sections inthe textbook The conceptual questions are also correlated

to relevant media and art from the book

TeamUP Integration Services

http://teamup.college.hmco.comHoughton Mifflin aims to provide customers with qualitytextbooks, technology, and superior training and implemen-tation services TeamUP, our integration program, offersflexible, personalized training and consultative services byphone, online, or on campus Experienced faculty advisorsand media specialists will assist you and your department

in using our products most effectively

Course-Management Software is available through WebCT

and Blackboard These two distributed learning systems

al-low instructors to create a virtual classroom without anyknowledge of HTML Features include: assessment tools, agradebook, online file exchange between instructors and stu-dents, online syllabi, and course descriptions The customized

Chemistry cartridges feature Test Bank questions, lecture

materials, and study aids related to the text

Print Supplements: For Instructors

Arena Zumdahl, and Steven S Zumdahl, presents detailedsolutions for all of the end-of-chapter exercises in the textfor the convenience of faculty and staff involved in instruc-tion and for instructors who wish their students to have so-lutions for all exercises Departmental approval is required

for the sale of the Complete Solutions Guide to students.

in-cludes suggestions for alternative orders of topics, suggested

responses to the Active Learning Questions, amplification

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To the Professor xiii

of strategies used in various chapters, lesson plans of media

resources correlated to section, answers to Reacts, and a

sec-tion on notes for teaching assistants

Uni-versity of Wisconsin—Madison, lists the sources for over

750 classroom demonstrations that can be used in general

chemistry courses Icons in the margins of the Instructor’s

Annotated Edition of the text key the demonstrations to their

corresponding text discussions

Seventh Edition, by James F Hall, contains tips including

hints on running experiments, approximate times for each

experiment, and answers to all prelab and postlab questions

posed in the laboratory guide

cre-ate a completely customized lab manual by mixing and

matching from 88 general chemistry labs—including all

the labs from Experimental Chemistry—and 56 labs for the

course in general, organic, and biochemistry At the

On-line Teaching Center, instructors search through the

data-base of labs, make their selections, organize the sequence

of the manual, and submit their order via the Internet

Cus-tomized, printed, and bound lab manuals are delivered to

the bookstore within weeks

Zum-dahl, and Gretchen Adams (available to adopters), offers a

printed version of more than 2000 exam questions, 10

per-cent of which are new to this edition, referenced to the

appropriate text section Questions are in multiple-choice,

open-ended, and true-false formats

adopters of the seventh edition of the text

Technology: For Students

Chemistry is supported by an array of learning tools designed

to help students succeed in their chemistry course It includes

the following media resources:

A passkey to the Online Study Center is bound into the

front of the textbook From the Online Study Center, students

have access to practice, visualization, and self-study aids

Visu-alization animations and video demonstrations help students see

key concepts, and each Visualization is accompanied by quiz

questions for students’ review A For Review section helps

students review key topics at a glance and includes video

demon-strations and animations for additional reinforcement

Flash-cards and ACE practice tests help students study key concepts

and problem-solve A molecule library, glossary, and interactive

periodic table are also available for support A Student CD, with

many of these Online Study Center resources, is available upon

request for students who do not have Internet access

Eduspace (powered by Blackboard), Houghton Mifflin’s

complete course-management solution, features algorithmic

end-of-chapter questions along with ChemWork interactive

online homework Through Eduspace, students can also accessthe Online Study Center and SMARTHINKING live, onlinetutoring Instructors who adopt Eduspace will receive a sepa-rate user guide for the program with a passkey to set up theircourse Students using Eduspace will also receive a separateuser guide and passkey

SMARTHINKING live, online tutoring is also availablefree with new books upon instructor request Students may alsopurchase stand-alone access to it SMARTHINKING providespersonalized, text-specific tutoring and is available during peakstudy hours when students need it most Limits apply; termsand hours of SMARTHINKING service are subject to change

Print Supplements: For Students

Urbana Written to be a self-study aid for students, this guideincludes alternate strategies for solving problems, supple-mental explanations for the most difficult material, and self-tests There are approximately 500 worked examples and

1200 practice problems (with answers), designed to give dents mastery and confidence

Arena Zumdahl, and Steven S Zumdahl, all of the sity of Illinois, Urbana, provides detailed solutions for half

Univer-of the end-Univer-of-chapter exercises (designated by the blue tion numbers) using the strategies emphasized in the text

ques-To ensure the accuracy of the solutions, this supplement and

the Complete Solutions Guide were checked independently

by several instructors

workbook can be used in lecture or recitation in tion with the instructor PowerPoint slides It provides a com-

conjunc-plete set of React questions with space for student answers.

Students can use the workbook as a self-study aid outside

of class

Qual-itative Analysis, by Steven S Zumdahl Successfully used

by thousands of students, this book offers thorough, by-step procedures for solving problems related to equi-libria taking place both in the gas phase and in solution.Containing hundreds of sample exercises, test exerciseswith complete solutions, and end-of-chapter exerciseswith answers, the text utilizes the same problem-solving

step-methods found in Chemistry and is an excellent source of

additional drill-type problems The last chapter presents

an exploratory qualitative analysis experiment with planations based on the principles of aqueous equilibria

of the University of Massachusetts—Lowell, provides an tensively revised laboratory program compatible with thetext The 48 experiments present a wide variety of chem-istry, and many experiments offer choices of procedures.Safety is strongly emphasized throughout the program

Trang 15

ex-Acknowledgments: This book represents the efforts of

many talented and dedicated people We particularly want to

thank Richard Stratton, Executive Editor, for his vision and

oversight of this project Richard’s knowledge, judgment, and

enthusiasm have contributed immeasurably to the success of

this text He is not only an outstanding editor but also one of

the nicest people in the business

We also want to thank Cathy Brooks, Senior Project

Edi-tor, who did a miraculous job of coordinating the production

of an incredibly complex project with grace and good humor

We also especially appreciate the excellent work of Rebecca

Berardy Schwartz, Developmental Editor, who managed the

re-vision process in a very supportive and organized manner

We are especially grateful to Tom Hummel, who managed

the revision of the end-of-chapter problems and the solutions

manuals Tom’s extensive experience teaching general

chem-istry and his high standards of accuracy and clarity have

resulted in great improvements in the quality of the problems

and the solutions in this edition In addition, we very much

ap-preciate the contributions of Don DeCoste, who has helped us

comprehend more clearly the difficulties students have with

conceptual understanding and who contributed the Challenge

Problems

We also extend our thanks to Jason Overby, who rendered

the electrostatic potential maps and who contributed the

Integrative Problems Our thanks and love also go to Leslie,

Steve, Whitney, Scott, Tyler, Sunshine, and Tony for their

con-tinuing support

Thanks to the others at Houghton Mifflin who supplied

valuable assistance on this revision: Jill Haber, Senior Art/Design

Coordinator; Sharon Donahue, Photo Researcher; Katherine

Greig, Senior Marketing Manager; Naveen Hariprasad,

Mar-keting Assistant; and Susan Miscio, Editorial Assistant

Special thanks go to the following people who helped

shape this edition by offering suggestions for its improvement:

Dawood Afzal, Truman State (media reviewer); Carol

Anderson, University of Connecticut—Avery Point (media

reviewer); Jeffrey R Appling, Clemson University (media

reviewer); Dave Blackburn, University of Minnesota;

Robert S Boikess, Rutgers University; Ken Carter, Truman

State (media reviewer); Bette Davidowitz, University of

Cape Town; Natalie Foster, Lehigh University; Tracy A

Halmi, Penn State Erie, The Behrend College; Carl A.Hoeger, UC—San Diego; Ahmad Kabbani, LebaneseAmerican University; Arthur Mar, University of Alberta;Jim McCormick, Truman State (media reviewer); RichardOrwell, Blue Ridge Community College (media reviewer);Jason S Overby, College of Charleston; Robert D Pike,The College of William and Mary; Daniel Raftery, PurdueUniversity; Jimmy Rogers, University of Texas—Arlington(media reviewer); Raymond Scott, Mary WashingtonCollege; Alan Stolzenberg, West Virginia University;

Rashmi Venkateswaran, University of Ottawa AP

reviewers: Annis Hapkiewicz, Okemos High School; Tina

Ohn-Sabatello, Maine Township HS East Interactive

Course Guide Reviewers: Lynne C Cary, Ph.D., Bethel

College; Craig C Martens, University of California—Irvine; Jeffrey P Osborne, Manchester College; Donald W.Shive, Muhlenberg College; Craig Sockwell, NorthwestShoals Community College; Richard Pennington, College

of St Mary Accuracy reviewers: Linda Bush (textbook

reviewer), Jon Booze (media reviewer)

Reviewers of the sixth edition:

Ramesh D Arasasingham, University of California—Irvine;Stanley A Bajue, Medgar Evans College, CUNY; V.G.Berner, New Mexico Junior College; Dave Blackburn,University of Minnesota; Steven R Boone, Central MissouriState University; Gary S Buckley, Cameron University;Lara L Chappell, SUNY College at Oswego; David Cramb,University of Calgary; Philip W Crawford, SoutheastMissouri State University; Philip Davis, University ofTennessee; Michael P Garoutte, Missouri Southern StateCollege; Daniel Graham, Loyola University; David R.Hawkes, Lambuth University; Dale Hawley, Kansas StateUniversity; Thomas B Higgins, Harold Washington College;John C Hogan, Louisiana State University; Donald P Land,University of California—Davis; Michael P Masingale,LeMoyne College; Julie T Millard, Colby College; Robert H.Paine, Rochester Institute of Technology; Brenda Ross,Cottey College; Jay S Shore, South Dakota State University;Richard T Toomey, Northwest Missouri State University;Robert Zoellner, Humboldt State University

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The major purpose of this book, of course, is to help you

learn chemistry However, this main thrust is closely linked to

two other goals: to show how important and how interesting

the subject is, and to show how to think like a chemist To solve

complicated problems the chemist uses logic, trial and error,

intuition, and, above all, patience A chemist is used to being

wrong The important thing is to learn from a mistake, recheck

assumptions, and try again A chemist thrives on puzzles that

seem to defy solutions

Many of you using this text do not plan to be practicing

chemists However, the nonchemist can benefit from the

chemist’s attitude Problem solving is important in all

profes-sions and in all walks of life The techniques you will learn

from this book will serve you well in any career you choose

Thus, we believe that the study of chemistry has much to offer

the nonmajor, including an understanding of many fascinating

and important phenomena and a chance to hone

problem-solving skills

This book attempts to present chemistry in a manner that

is sensible to the novice Chemistry is not the result of an

in-spired vision It is the product of countless observations and

many attempts, using logic and trial and error, to account for

these observations In this book the concepts are developed in

a natural way: The observations come first and then models are

constructed to explain the observed behavior

Models are a major focus in this book The uses and

lim-itations of models are emphasized, and science is treated as a

human activity, subject to all the normal human foibles

Mis-takes are discussed as well as successes

A central theme of this book is a thoughtful, systematic

approach to problem solving Learning encompasses much

more than simply memorizing facts Truly educated people use

their factual knowledge as a starting point—a base for creative

approaches to solving problems

Read through the material in the text carefully For most

concepts, illustrations or photos will help you visualize what

is going on To further help you visualize concepts by using

animations and videos, we have included Visualization

exer-cises on the Online Study Center or on an optional free CD

Icons in the text margin signal that there is companion

mater-ial available on the CD

Often a given type of problem is “walked through” in the

text before the corresponding Sample Exercises appear

Strate-gies for solving problems are given throughout the text

Thoroughly examine the Sample Exercises and the lem-solving strategies The strategies summarize the approachtaken in the text; the Sample Exercises follow the strategiesstep-by-step Schematics in Chapter 15 also illustrate thelogical pathways to solving aqueous equilibrium problems.Throughout the text, we have used margin notes to high-light key points, to comment on an application of the textmaterial, or to reference material in other parts of the book.Chemical Impact, the boxed feature that appears frequentlythroughout the text, discusses especially interesting applica-tions of chemistry to the everyday world

prob-Each chapter has a summary and key terms list for review,and the glossary gives a quick reference for definitions.Learning chemistry requires working the end-of-chapterexercises assigned by your professor Answers to exercisesdenoted by blue question numbers are in the back of thebook, and complete solutions to those exercises are in the

Partial Solutions Guide To help you assess your level of

proficiency, the Online Study Center (college.hmco.com/PIC/zumdahl7e) offers quizzes and electronic homework assign-ments that feature instant feedback

The Study Guide contains extra practice problems and many worked examples The supplement, Solving Equilibrium

Problems with Applications to Qualitative Analysis, reinforces

in great detail the text’s step-by-step approach to solvingequilibrium problems and contains many worked examples andself-quiz questions

It is very important to use the exercises and electronichomework assignments to your best advantage Your main goal

should not be to simply get the correct answer but to

under-stand the process for getting the answer Memorizing the

so-lutions for specific problems is not a very good way to preparefor an exam There are too many pigeonholes required to coverevery possible problem type Look within the problem for thesolution Use the concepts you have learned along with a sys-tematic, logical approach to find the solution Learn to trustyourself to think it out You will make mistakes, but the im-portant thing is to learn from these errors The only way to gainconfidence is to do lots of practice problems and use these todiagnose your weaknesses

Be patient and thoughtful and work hard to understandrather than simply memorize We wish you an interesting andsatisfying year

To the Student

Trang 17

Features of Chemistry

The Contents gives students an

overview of the topics to come

Conceptual Understanding

and Problem Solving

Fundamental Properties of Models

nature works A model does not equal reality.

on speculation and are always oversimplifications.

models, we “patch” them and thus add more detail.

be-ally involve very restrictive assumptions and can be expected to yield only qualitative expecting to get an accurate mass for a diamond using a bathroom scale.

For a model to be used effectively, we must understand its strengths and nesses and ask only appropriate questions An illustration of this point is the simple though this model correctly predicts the configuration for most atoms, chromium and configurations of chromium and copper result from complex electron interactions that should discard the simple model that is so useful for most atoms Instead, we must apply it with caution and not expect it to be correct in every case.

makes a wrong prediction, it usually means we do not understand some this when you get back your next chemistry test.)

In this section we will consider the energies associated with various types of bonds and One important consideration is to establish the sensitivity of a particular type of bond methane:

Process Energy Required (kJ/mol)

8.13 Molecular Structure: The VSEPR Model

The structures of molecules play a very important role in determining their chemical

prop-erties As we will see later, this is particularly important for biological molecules; a slight

change in the structure of a large biomolecule can completely destroy its usefulness to a

cell or may even change the cell from a normal one to a cancerous one.

Many accurate methods now exist for determining molecular structure, the

three-dimensional arrangement of the atoms in a molecule These methods must be used if

precise information about structure is required However, it is often useful to be able to

predict the approximate molecular structure of a molecule In this section we consider a

simple model that allows us to do this This model, called the valence shell electron-pair

repulsion (VSEPR) model, is useful in predicting the geometries of molecules formed

from nonmetals The main postulate of this model is that the structure around a given

atom is determined principally by minimizing electron-pair repulsions The idea here is

that the bonding and nonbonding pairs around a given atom will be positioned as far apart

as possible To see how this model works, we will first consider the molecule BeCl 2 , which

has the Lewis structure

Avogadro’s Law

Suppose we have a 12.2-L sample containing 0.50 mol oxygen gas (O2) at a pressure of

1 atm and a temperature of 25C If all this O2 were converted to ozone (O3) at the same temperature and pressure, what would be the volume of the ozone?

Solution

The balanced equation for the reaction is

To calculate the moles of O3 produced, we must use the appropriate mole ratio:

Avogadro’s law states that V  an, which can be rearranged to give

Since a is a constant, an alternative representation is

where V1 is the volume of n1moles of O2gas and V2 is the volume of n2moles of O3 gas.

In this case we have

Solving for V2gives

Reality Check:Note that the volume decreases, as it should, since fewer moles of gas molecules will be present after O2 is converted to O3.

See Exercises 5.35 and 5.36.

V2  an2

n1b V1 a0.33 mol0.50 mol b 12.2 L  8.1 L

FIGURE 5.10

These balloons each hold 1.0 L of gas at

25C and 1 atm Each balloon contains

Sample Exercises model a step-by-step approach

to solving problems Cross-references to similarend-of-chapter exercises are provided at the end of

each Sample Exercise Reality Checks appear after

the solutions in selected exercises, helpingstudents evaluate their answers to ensure that theyare reasonable

By stressing thelimitations and uses of

scientific models, the

authors show studentshow chemists thinkand work

The authors’ emphasis on

modeling (or chemical theories)

throughout the text addresses the

problem of rote memorization by

helping students better

understand and appreciate the

process of scientific thinking

xvi

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in water For example, virtually all the chemistry that makes life possible occurs in an aqueous environment Also, various medical tests involve aqueous reactions, depending sugar, cholesterol, and iron, analyses for specific chemical markers allow detection of many diseases before obvious symptoms occur.

Aqueous chemistry is also important in our environment In recent years, nation of the groundwater by substances such as chloroform and nitrates has been widely publicized Water is essential for life, and the maintenance of an ample supply of clean water is crucial to all civilization.

contami-To understand the chemistry that occurs in such diverse places as the human body, the atmosphere, the groundwater, the oceans, the local water treatment plant, your hair as you shampoo it, and so on, we must understand how substances dissolved in water react with each other.

However, before we can understand solution reactions, we need to discuss the nature

of solutions in which water is the dissolving medium, or solvent These solutions are called

solved in water and various types of reactions that occur among these substances You very well for reactions that take place in aqueous solutions To understand the types of This requires an understanding of the nature of water.

Water is one of the most important substances on earth It is essential for sustaining the helps moderate the earth’s temperature; it cools automobile engines, nuclear power earth’s surface and a medium for the growth of a myriad of creatures we use as food; and much more.

One of the most valuable properties of water is its ability to dissolve many different substances For example, salt “disappears” when you sprinkle it into the water used to cook vegetables, as does sugar when you add it to your iced tea In each case the “dis- solid dissolves? To understand this process, we need to consider the nature of water Liquid

or V-shaped, with an HOOOH angle of approximately 105 degrees:

The OOH bonds in the water molecule are covalent bonds formed by electron ing between the oxygen and hydrogen atoms However, the electrons of the bond are not gen has a greater attraction for electrons than does hydrogen If the electrons were shared the number of electrons around each would equal the number of protons in that nucleus.

shar-H H

CHEMICAL IMPACT

The Chemistry of Air Bags

Most experts agree that air bags represent a very

impor-tant advance in automobile safety These bags, which

are stored in the auto’s steering wheel or dash, are designed

to inflate rapidly (within about 40 ms) in the event of a crash,

cushioning the front-seat occupants against impact The bags

then deflate immediately to allow vision and movement

af-ter the crash Air bags are activated when a severe

deceler-ation (an impact) causes a steel ball to compress a spring

and electrically ignite a detonator cap, which, in turn, causes

sodium azide (NaN 3 ) to decompose explosively, forming

sodium and nitrogen gas:

This system works very well and requires a relatively small

amount of sodium azide (100 g yields 56 L N 2(g) at 25C

and 1.0 atm).

When a vehicle containing air bags reaches the end of

its useful life, the sodium azide present in the activators must

be given proper disposal Sodium azide, besides being

ex-plosive, has a toxicity roughly equal to that of sodium

Inflated air bags.

Chemical Impact boxes

describe current applications

of chemistry These interest boxes cover suchtopics as preserving works ofart, molecules as a means ofcommunication, and the heat

special-of chili peppers

xvii

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346 Chapter Eight Bonding: General Concepts

more negative than that for combining gaseous Naand Fions to form NaF(s) Thus the

energy released in forming a solid containing Mg2and O2ions rather than Mgand

Oions more than compensates for the energies required for the processes that produce the Mg2and O2ions.

If there is so much lattice energy to be gained in going from singly charged to doubly charged ions in the case of magnesium oxide, why then does solid sodium fluoride contain Na  and F  ions rather than Na 2 and F 2 ions? We can answer this question by recognizing that both Na  and F  ions have the neon electron configura- tion Removal of an electron from Na  requires an extremely large quantity of energy

(4560 kJ/mol) because a 2p electron must be removed Conversely, the addition of an

electron to Fwould require use of the relatively high-energy 3s orbital, which is also

an unfavorable process Thus we can say that for sodium fluoride the extra energy required to form the doubly charged ions is greater than the gain in lattice energy that would result.

This discussion of the energies involved in the formation of solid ionic compounds illustrates that a variety of factors operate to determine the composition and structure of gies required to form highly charged ions and the energy released when highly charged ions combine to form the solid.

8.6 Partial Ionic Character of Covalent Bonds

Recall that when atoms with different electronegativities react to form molecules, the trons are not shared equally The possible result is a polar covalent bond or, in the case

elec-of a large electronegativity difference, a complete transfer elec-of one or more electrons to form ions The cases are summarized in Fig 8.12.

How well can we tell the difference between an ionic bond and a polar covalent bond?

The only honest answer to this question is that there are probably no totally ionic bonds

of the percent ionic character for the bonds of various binary compounds in the gas phase.

These calculations are based on comparisons of the measured dipole moments for cules of the type X—Y with the calculated dipole moments for the completely ionic case,

mole-XY The percent ionic character of a bond can be defined as

Application of this definition to various compounds (in the gas phase) gives the results shown in Fig 8.13, where percent ionic character is plotted versus the difference in the electronegativity values of X and Y Note from this plot that ionic character increases with electronegativity difference, as expected However, none of the bonds reaches 100% ionic character, even though compounds with the maximum possible electronegativity differ- ences are considered Thus, according to this definition, no individual bonds are com- pletely ionic This conclusion is in contrast to the usual classification of many of these ionic character are normally considered to be ionic solids Recall, however, the results in Fig 8.13 are for the gas phase, where individual XY molecules exist These results can- not necessarily be assumed to apply to the solid state, where the existence of ions is fa- vored by the multiple ion interactions.

Another complication in identifying ionic compounds is that many substances contain polyatomic ions For example, NH4Cl contains NH4and Clions, and Na2SO4 contains Naand SO4ions The ammonium and sulfate ions are held together

by covalent bonds Thus, calling NH4Cl and Na2SO4 ionic compounds is somewhat ambiguous.

Percent ionic character of a bond  ameasured dipole moment of X¬Y

calculated dipole moment of X  Y b  100%

FIGURE 8.12

The three possible types of bonds: (a) a

covalent bond formed between identical F

atoms; (b) the polar covalent bond of HF,

with both ionic and covalent components;

and (c) an ionic bond with no electron

Since the equation for lattice energy

con-tains the product Q1Q2, the lattice energy

for a solid with 2 and 2 ions should

be four times that for a solid with 1

and 1 ions That is,

For MgO and NaF, the observed ratio of

lattice energies (see Fig 8.11) is

3916 kJ

923 kJ 4.24

122122

112112 4

Electrostatic potential maps help

students visualize the distribution of

charge in molecules

FIGURE 4.17

Photos and accompanying molecular-level representations illustrating the reaction of KCl(aq) with AgNO3(aq) to form AgCl(s) Note that it is not

possible to have a photo of the mixed solution before the reaction occurs, because it is an imaginary step that we use to help visualize the reaction Actually, the reaction occurs immediately when the two solutions are mixed.

the “micro-macro”

connection

Visualization animations and video

demonstrations help studentsfurther understand and visualizechemical concepts Animations andvideos (Visualizations) are found

via the Online Study Center and

Online Teaching Center, and HM ClassPresent instructor CD.

xviii

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4 As you increase the temperature of a gas in a sealed, rigid

con-tainer, what happens to the density of the gas? Would the results

a piston at constant pressure? (See Figure 5.17.)

5 A diagram in a chemistry book shows a magnified view of a

flask of air as follows:

What do you suppose is between the dots (the dots represent air molecules)?

6 If you put a drinking straw in water, place your finger over the

opening, and lift the straw out of the water, some water stays in the straw Explain.

7 A chemistry student relates the following story: I noticed my

tires were a bit low and went to the gas station As I was filling noticed the tires because the volume was low, and I realized that

“Hmmm,” I thought, “that goes against what I learned in portional.” What is the fault in the logic of the chemistry student

chem-be inversely related (draw pictures and use the KMT).

8 Chemicals X and Y (both gases) react to form the gas XY, but it

takes a bit of time for the reaction to occur Both X and Y are

the volume As the reaction occurs, what happens to the volume

of the container? (See Fig 5.18.)

9 Which statement best explains why a hot-air balloon rises when

the air in the balloon is heated?

a According to Charles’s law, the temperature of a gas is

directly related to its volume Thus the volume of the balloon

b Hot air rises inside the balloon, and this lifts the balloon.

c The temperature of a gas is directly related to its pressure.

The pressure therefore increases, and this lifts the balloon.

d Some of the gas escapes from the bottom of the balloon, thus

decreasing the mass of gas in the balloon This decreases the density of the gas in the balloon, which lifts the balloon.

e Temperature is related to the root mean square velocity of the

gas molecules Thus the molecules are moving faster, hitting the balloon more, and thus lifting the balloon.

Justify your choice, and for the choices you did not pick, explain what is wrong with them.

Active Learning Questions

These questions are designed to be used by groups of students in class The

discussion and peer teaching The real value of these questions is the learning

that occurs while students talk to each other about chemical concepts.

1 Consider the following apparatus: a test tube covered with a

non-permeable elastic membrane inside a container that is closed with

a cork A syringe goes through the cork.

a As you push down on the syringe, how does the membrane

covering the test tube change?

b You stop pushing the syringe but continue to hold it down.

In a few seconds, what happens to the membrane?

2 Figure 5.2 shows a picture of a barometer Which of the following

statements is the best explanation of how this barometer works?

tube until the air pressure inside and outside the tube is equal.

b Air pressure inside the tube causes the mercury to move in the

tube until the air pressure inside and outside the tube is equal.

c Air pressure outside the tube counterbalances the weight of

the mercury in the tube.

d Capillary action of the mercury causes the mercury to go up

the tube.

e The vacuum that is formed at the top of the tube holds up the

mercury.

Justify your choice, and for the choices you did not pick, explain

what is wrong with them Pictures help!

3 The barometer below shows the level of mercury at a given

at-mospheric pressure Fill all the other barometers with mercury

for that same atmospheric pressure Explain your answer.

mm Hg torr standard atmosphere pascal

Section 5.2

Boyle’s law ideal gas Charles’s law Avogadro’s law

Section 5.5

Dalton’s law of partial pressures partial pressure mole fraction

Section 5.6

kinetic molecular theory (KMT) root mean square velocity joule

Section 5.7

diffusion effusion Graham’s law of effusion

Section 5.8

real gas van der Waals equation

Section 5.10

atmosphere air pollution photochemical smog acid rain

Ideal gas law: PV  nRT

Dalton’s law of partial pressures: Ptotal P1 P2 P3 , where Pnrepresents

the partial pressure of component n in a mixture of gases

Kinetic molecular theory (KMT)

䊉 Model that accounts for ideal gas behavior

䊉 The particles in any gas sample have a range of velocities

䊉 The root mean square (rms) velocity for a gas represents the average of the squares

of the particle velocities

䊉 Diffusion: the mixing of two or more gases

䊉 Effusion: the process in which a gas passes through a small hole into an empty chamber

Real gas behavior

䊉 Real gases behave ideally only at high temperatures and low pressures

䊉 Understanding how the ideal gas equation must be modified to account for real gas behavior helps us understand how gases behave on a molecular level

䊉 Van der Waals found that to describe real gas behavior we must consider particle interactions and particle volumes

questions Key Terms are

printed in bold type andare defined where theyfirst appear They are alsogrouped at the end of thechapter and in the

Glossary at the back of

the text

226 Chapter Five Gases

If 2.55  10 2mL of NO(g) is isolated at 29C and 1.5 atm, what

amount (moles) of UO 2 was used in the reaction?

128 Silane, SiH4 , is the silicon analogue of methane, CH 4 It is prepared industrially according to the following equations:

a If 156 mL of HSiCl3(d 1.34 g/mL) is isolated when 15.0 L

of HCl at 10.0 atm and 35C is used, what is the percent yield

of HSiCl 3 ?

b When 156 mL of HSiCl3 is heated, what volume of SiH 4 at 10.0 atm and 35C will be obtained if the percent yield of the reaction is 93.1%?

129.Solid thorium(IV) fluoride has a boiling point of 1680C What

is the density of a sample of gaseous thorium(IV) fluoride at its Which gas will effuse faster at 1680C, thorium(IV) fluoride or uranium(III) fluoride? How much faster?

130 Natural gas is a mixture of hydrocarbons, primarily methane

(CH 4 ) and ethane (C 2 H 6 ) A typical mixture might have

 methane  0.915 and  ethane  0.085 What are the partial sures of the two gases in a 15.00-L container of natural gas at 20.C and 1.44 atm? Assuming complete combustion of both gases in the natural gas sample, what is the total mass of water formed?

pres-Marathon Problem*

This problem is designed to incorporate several concepts and techniques students to help facilitate problem-solving skills.

131 Use the following information to identify element A and

com-pound B, then answer questions a and b.

An empty glass container has a mass of 658.572 g It has a mass of 659.452 g after it has been filled with nitrogen gas at a pressure of 790 torr and a temperature of 15C When the con- tainer is evacuated and refilled with a certain element (A) at a pressure of 745 torr and a temperature of 26C, it has a mass of 660.59 g.

Compound B, a gaseous organic compound that consists of 85.6% carbon and 14.4% hydrogen by mass, is placed in a stain- placed in a constant-temperature bath at 22C The pressure in the vessel is 11.98 atm In the bottom of the vessel is a container impregnated with sodium hydroxide; it quantitatively absorbs carbon dioxide:

a Explain why the balloon would float when heated Make sure

to discuss which factors change and which remain constant, and why this matters Be complete.

b Above what temperature would you heat the balloon so that

be-a Will the temperature in the hot-air balloon have to be higher

or lower than 25C? Explain.

b Calculate the temperature of the air required for the hot-air

balloon to provide the same lift as the helium balloon at 1.00 atm and 25C Assume atmospheric conditions are 1.00 atm and 25C.

124 We state that the ideal gas law tends to hold best at low

pres-sures and high temperatures Show how the van der Waals tion simplifies to the ideal gas law under these conditions.

equa-125.Atmospheric scientists often use mixing ratios to express the expressed as ppmv (parts per million volume):

con-On a recent autumn day, the concentration of carbon monoxide

in the air in downtown Denver, Colorado, reached 3.0  10 2

ppmv The atmospheric pressure at that time was 628 torr, and the temperature was 0C.

a What was the partial pressure of CO?

b What was the concentration of CO in molecules per cubic

centimeter?

126 Nitrogen gas (N2 ) reacts with hydrogen gas (H 2 ) to form monia gas (NH 3 ) You have nitrogen and hydrogen gases in a 15.0-L container fitted with a movable piston (the piston allows stant inside the container) Initially the partial pressure of each that the reaction goes to completion.

am-a Calculate the partial pressure of ammonia in the container

af-ter the reaction has reached completion.

b Calculate the volume of the container after the reaction has

reached completion.

Integrative Problems

These problems require the integration of multiple concepts to find the solutions.

127.In the presence of nitric acid, UO 2 undergoes a redox process.

It is converted to UO 2  and nitric oxide (NO) gas is produced according to the following unbalanced equation:

NO 3 1aq2  UO21aq2 ¡ NO1g2  UO2 1aq2

ppmv of X vol of X at STP

total vol of air at STP  10 6

*Used with permission from the Journal of Chemical Education, Vol 68,

Education, Inc.

Questions give students an

opportunity to review key

concepts; Exercises (paired and

organized by topic) reinforcestudents’ understanding of each

section; Additional Exercises

require students to identify andapply the appropriate concepts

themselves; Challenge Problems

take students one step furtherand challenge students morerigorously than Additional

Exercises; Integrative Problems

combine concepts from multiple

chapters; Marathon Problems

also combine concepts frommultiple chapters, and they arethe most challenging problems inthe end-of-chapter material

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Developed by the Zumdahls to

reinforce the approach of the book,

ChemWork interactive online

homework offers problems

accompanied by hints to help

students as they think through

each problem ChemWork

assignments are offered in

Eduspace—Houghton Mifflin’s

course-management system

The Online Study Center features

Visualization practice exercises.

Visualizations include animationsand video demonstrations thathelp students to furtherunderstand chemical concepts

Each Visualization is accompanied

by quiz questions

xx

Algorithmic, chapter exercises fromthe text also appear in

end-of-Eduspace Exercises

also include helpfullinks to art, tables, andequations from thetextbook

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HM ClassPrep with HM Testing (powered by Diploma) CD is a

cross-platform CD that contains extensive text-specific resources

for instructors to incorporate into their lecture presentations

These customizable assets include PowerPoint slides, Word files

of the printed Test Bank and Solutions Manual, figures from the

text, the Instructor’s Resource Guide and more HM Testing

(powered by Diploma) is Houghton Mifflin’s new flexible

test-editing program, which features algorithmically generated

ques-tions, conceptual quesques-tions, and factual questions coded by level

of difficulty to allow

you to more easily

choose appropriate test

items Select from 2400

test items designed to

measure the concepts

and principles covered

in the seventh edition

HM ClassPresent

includes animations

and video

demons-trations that can be

used to illustrate

concepts and ideas that

will help students

further understand and visualize chemical concepts Animations

and videos can be projected directly from the CD, exported

to your computer, and also come embedded in PowerPoint

files

Online Teaching Center for Chemistry offers access to

lecture preparation materials; PowerPoint presentation

resources; JPEGs of virtually all text illustrations, tables, and

photos; video demonstrations and animations; molecule

library with CHIME; as well as service and support Also

included on the Online Teaching Center, you will find

classroom response-system slides These slides allow you

to get on-the-spot feedback on how well your students are

grasping key concepts

Eduspace, featuring online homework, is Houghton

Mifflin’s course-management system Eduspace allows for

online delivery of course materials, chat and discussion

tools, and includes two types of algorithmic online

homework: ChemWork and end-of-chapter exercises.

ChemWork helps students learn the process of problem

solving with interactive hints that help students think

through each problem

Media Resources for Instructors

xxi

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The Online Study Center supports the goals

of the seventh edition with visualization,

practice, and study aids The Visualizations use

animations and video demonstrations to helpstudents see the chemistry concepts, and each

Visualization is accompanied by a set of quiz

questions so that students can test theirknowledge of the concept

The Online Study Center also includes aninteractive review for each chapter, flashcards

of key terms, and ACE practice tests, which

help students prepare for quizzes and exams.Many of the resources on the Online StudyCenter are also available on the optional free,student CD-ROM

Students get access to live, online

help through SMARTHINKING™.

E-structors are available when studentsneed it the most and help studentsproblem-solve rather than supplyanswers Available free with new books

on instructor’s request Also availablevia Eduspace

xxii

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Contents

1.1 Chemistry: An Overview

• Science: A Process for

Understanding Nature and

• Precision and Accuracy

1.5 Significant Figures and

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When you start your car, do you think about chemistry? Probably not, but youshould The power to start your car is furnished by a lead storage battery How does thisbattery work, and what does it contain? When a battery goes dead, what does that mean?

If you use a friend’s car to “jump start” your car, did you know that your battery couldexplode? How can you avoid such an unpleasant possibility? What is in the gasoline thatyou put in your tank, and how does it furnish the energy to drive to school? What is thevapor that comes out of the exhaust pipe, and why does it cause air pollution? Your car’sair conditioner might have a substance in it that is leading to the destruction of the ozonelayer in the upper atmosphere What are we doing about that? And why is the ozone layerimportant anyway?

All these questions can be answered by understanding some chemistry In fact, we’llconsider the answers to all these questions in this text

Chemistry is around you all the time You are able to read and understand this tence because chemical reactions are occurring in your brain The food you ate for break-fast or lunch is now furnishing energy through chemical reactions Trees and grass growbecause of chemical changes

sen-Chemistry also crops up in some unexpected places When archaeologist Luis Alvarezwas studying in college, he probably didn’t realize that the chemical elements iridium andniobium would make him very famous when they helped him solve the problem of thedisappearing dinosaurs For decades scientists had wrestled with the mystery of why thedinosaurs, after ruling the earth for millions of years, suddenly became extinct 65 millionyears ago In studying core samples of rocks dating back to that period, Alvarez and hiscoworkers recognized unusual levels of iridium and niobium in these samples—levelsmuch more characteristic of extraterrestrial bodies than of the earth Based on theseobservations, Alvarez hypothesized that a large meteor hit the earth 65 million years ago,changing atmospheric conditions so much that the dinosaurs’ food couldn’t grow, and theydied—almost instantly in the geologic timeframe

Chemistry is also important to historians Did you realize that lead poisoning bly was a significant contributing factor to the decline of the Roman Empire? The Romanshad high exposure to lead from lead-glazed pottery, lead water pipes, and a sweetening

proba-syrup called sapa that was prepared by boiling down grape juice in lead-lined vessels It

turns out that one reason for sapa’s sweetness was lead acetate (“sugar of lead”) thatformed as the juice was cooked down Lead poisoning with its symptoms of lethargy andmental malfunctions certainly could have contributed to the demise of the Roman society.Chemistry is also apparently very important in determining a person’s behavior.Various studies have shown that many personality disorders can be linked directly toimbalances of trace elements in the body For example, studies on the inmates at Stat-eville Prison in Illinois have linked low cobalt levels with violent behavior Lithium saltshave been shown to be very effective in controlling the effects of manic depressive dis-ease, and you’ve probably at some time in your life felt a special “chemistry” for anotherperson Studies suggest there is literally chemistry going on between two people who areattracted to each other “Falling in love” apparently causes changes in the chemistry ofthe brain; chemicals are produced that give that “high” associated with a new relation-ship Unfortunately, these chemical effects seem to wear off over time, even if the rela-tionship persists and grows

The importance of chemistry in the interactions of people should not really surprise

us, since we know that insects communicate by emitting and receiving chemical signals via

molecules called pheromones For example, ants have a very complicated set of chemical

1

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signals to signify food sources, danger, and so forth Also, various female sex attractantshave been isolated and used to lure males into traps to control insect populations It wouldnot be surprising if humans also emitted chemical signals that we were not aware of on

a conscious level Thus chemistry is pretty interesting and pretty important The main goal

of this text is to help you understand the concepts of chemistry so that you can better preciate the world around you and can be more effective in whatever career you choose

ap-1.1 Chemistry: An Overview

Since the time of the ancient Greeks, people have wondered about the answer to the tion: What is matter made of? For a long time humans have believed that matter is com-posed of atoms, and in the previous three centuries we have collected much indirectevidence to support this belief Very recently, something exciting has happened—for thefirst time we can “see” individual atoms Of course, we cannot see atoms with the nakedeye but must use a special microscope called a scanning tunneling microscope (STM).Although we will not consider the details of its operation here, the STM uses an electroncurrent from a tiny needle to probe the surface of a substance The STM pictures of severalsubstances are shown in Fig 1.1 Notice how the atoms are connected to one another by

ques-“bridges,” which, as we will see, represent the electrons that interconnect atoms

In addition to “seeing” the atoms in solids such as salt, we have learned how to late and view a single atom For example, the tiny white dot in the center of Fig 1.2 is asingle mercury atom that is held in a special trap

iso-So, at this point, we are fairly sure that matter consists of individual atoms The ture of these atoms is quite complex, and the components of atoms don’t behave much

na-like the objects we see in the world of our experience We call this world the macroscopic

world—the world of cars, tables, baseballs, rocks, oceans, and so forth One of the main

jobs of a scientist is to delve into the macroscopic world and discover its “parts.” Forexample, when you view a beach from a distance, it looks like a continuous solid substance

As you get closer, you see that the beach is really made up of individual grains of sand

(c)

FIGURE 1.1

(a) The surface of a single grain of table

salt (b) An oxygen atom (indicated by

arrow) on a gallium arsenide surface.

(c) Scanning tunneling microscope image

showing rows of ring-shaped clusters of

benzene molecules on a rhodium surface.

Each “doughnut”-shaped image represents

a benzene molecule.

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1.1 Chemistry: An Overview 3

As we examine these grains of sand, we find they are composed of silicon and oxygenatoms connected to each other to form intricate shapes (see Fig 1.3) One of the mainchallenges of chemistry is to understand the connection between the macroscopic world

that we experience and the microscopic world of atoms and molecules To truly

under-stand chemistry you must learn to think on the atomic level We will spend much time inthis text helping you learn to do that

One of the amazing things about our universe is that the tremendous variety of stances we find there results from only about 100 different kinds of atoms You can think

sub-of these approximately 100 atoms as the letters in an alphabet out sub-of which all the “words”

in the universe are made It is the way the atoms are organized in a given substance thatdetermines the properties of that substance For example, water, one of the most commonand important substances on earth, is composed of two types of atoms: hydrogen andoxygen There are two hydrogen atoms and one oxygen atom bound together to form thewater molecule:

When an electric current passes through it, water is decomposed to hydrogen and oxygen

These chemical elements themselves exist naturally as diatomic (two-atom) molecules:

We can represent the decomposition of water to its component elements, hydrogen andoxygen, as follows:

Notice that it takes two molecules of water to furnish the right number of oxygen and drogen atoms to allow for the formation of the two-atom molecules This reaction explains

hy-one oxygen molecule written O2

two water molecules written 2H2O

electric current

two hydrogen molecules written 2H2

written O2oxygen molecule

written H2hydrogen molecule

hydrogen atom

oxygen atom

water molecule

FIGURE 1.2

A charged mercury atom shows up as a

tiny white dot (indicated by the arrow).

O Si

FIGURE 1.3

Sand on a beach looks uniform from a

distance, but up close the irregular sand

grains are visible, and each grain is

com-posed of tiny atoms.

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why the battery in your car can explode if you jump start it improperly When you hook upthe jumper cables, current flows through the dead battery, which contains water (and otherthings), and causes hydrogen and oxygen to form by decomposition of some of the water.

A spark can cause this accumulated hydrogen and oxygen to explode, forming water again

This example illustrates two of the fundamental concepts of chemistry: (1) matter is posed of various types of atoms, and (2) one substance changes to another by reorganiz-ing the way the atoms are attached to each other

com-These are core ideas of chemistry, and we will have much more to say about them

O2

2H2O spark

2H2

The importance of chemistry can show up in some unusual

places For example, a knowledge of chemistry is crucial

to authenticating, preserving, and restoring art objects The

J Paul Getty Museum in Los Angeles has a state-of-the-art

chemical laboratory that costs many millions of dollars and

employs many scientists The National Gallery of Art (NGA)

in Washington, D.C., also operates a highly sophisticated

laboratory that employs 10 people: five chemists, a botanist,

an art historian, a technician with a chemistry degree, and

two fellows (interns)

One of the chemists at NGA is Barbara Berrie, who

spe-cializes in identifying paint pigments One of her duties is to

analyze a painting to see whether the paint pigments are

ap-propriate for the time the picture was supposedly painted and

consistent with the pigments known to be used by the artist

given credit for the painting This analysis is one way in which

paintings can be authenticated One of Berrie’s recent projects

was to analyze the 1617 oil painting St Cecilia and an Angel.

Her results showed the painting was the work of two artists

of the time, Orazio Gentileschi and Giovanni Lanfranco

Originally the work was thought to be by Gentileschi alone

Berrie is also working to define the range of colors used

by water colorist Winslow Homer (the NGA has 30 Homer

paintings in its collection) and to show how his color palette

changed over his career In addition, she is exploring how

acidity affects the decomposition of a particular deep green

transparent pigment (called copper resinate) used by Italian

Renaissance artists so that paintings using this pigment can

be better preserved

Berrie says, “The chemistry I do is not hot-dog

chem-istry, just good old-fashioned general chemistry.”

CHEMICAL IMPACT

The Chemistry of Art

Dr Barbara Berrie of the National Gallery of Art is shown analyzing the glue used in the wooden supports for a 14th century altar piece.

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1.2 The Scientific Method 5

Science: A Process for Understanding Nature and Its Changes

How do you tackle the problems that confront you in real life? Think about your trip toschool If you live in a city, traffic is undoubtedly a problem you confront daily How doyou decide the best way to drive to school? If you are new in town, you first get a mapand look at the possible ways to make the trip Then you might collect information frompeople who know the area about the advantages and disadvantages of various routes Based

on this information, you probably try to predict the best route However, you can findthe best route only by trying several of them and comparing the results After a fewexperiments with the various possibilities, you probably will be able to select the bestway What you are doing in solving this everyday problem is applying the same processthat scientists use to study nature The first thing you did was collect relevant data Thenyou made a prediction, and then you tested it by trying it out This process contains thefundamental elements of science

1 Making observations (collecting data)

2 Making a prediction (formulating a hypothesis)

3 Doing experiments to test the prediction (testing the hypothesis)

Scientists call this process the scientific method We will discuss it in more detail in

the next section One of life’s most important activities is solving problems—not “plugand chug” exercises, but real problems—problems that have new facets to them, thatinvolve things you may have never confronted before The more creative you are atsolving these problems, the more effective you will be in your career and your per-sonal life Part of the reason for learning chemistry, therefore, is to become a betterproblem solver Chemists are usually excellent problem solvers, because to masterchemistry, you have to master the scientific approach Chemical problems are frequentlyvery complicated—there is usually no neat and tidy solution Often it is difficult toknow where to begin

1.2 The Scientific Method

Science is a framework for gaining and organizing knowledge Science is not simply a

set of facts but also a plan of action—a procedure for processing and understanding

cer-tain types of information Scientific thinking is useful in all aspects of life, but in this text

we will use it to understand how the chemical world operates As we have said in our vious discussion, the process that lies at the center of scientific inquiry is called the

pre-scientific method There are actually many pre-scientific methods, depending on the nature

of the specific problem under study and on the particular investigator involved However,

it is useful to consider the following general framework for a generic scientific method(see Fig 1.4):

Steps in the Scientific Method

1 Making observations Observations may be qualitative (the sky is blue; water

is a liquid) or quantitative (water boils at 100C; a certain chemistry book

weighs 2 kilograms) A qualitative observation does not involve a number.

A quantitative observation (called a measurement) involves both a number and a unit.

2 Formulating hypotheses A hypothesis is a possible explanation for an observation.

3 Performing experiments An experiment is carried out to test a hypothesis This

involves gathering new information that enables a scientist to decide whether

Experiment Prediction

Observation Hypothesis Experiment

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the hypothesis is valid—that is, whether it is supported by the new information learned from the experiment Experiments always produce new observations, and this brings the process back to the beginning again.

To understand a given phenomenon, these steps are repeated many times, gradually cumulating the knowledge necessary to provide a possible explanation of the phenomenon

ac-Scientific Models

Once a set of hypotheses that agrees with the various observations is obtained, the

hy-potheses are assembled into a theory A theory, which is often called a model, is a set of

tested hypotheses that gives an overall explanation of some natural phenomenon

It is very important to distinguish between observations and theories An observation

is something that is witnessed and can be recorded A theory is an interpretation—a possible explanation of why nature behaves in a particular way Theories inevitably change

as more information becomes available For example, the motions of the sun and starshave remained virtually the same over the thousands of years during which humans havebeen observing them, but our explanations—our theories—for these motions have changedgreatly since ancient times (See the Chemical Impact on Observations, Theories, and thePlanets on the Web site.)

The point is that scientists do not stop asking questions just because a given ory seems to account satisfactorily for some aspect of natural behavior They continuedoing experiments to refine or replace the existing theories This is generally done byusing the currently accepted theory to make a prediction and then performing anexperiment (making a new observation) to see whether the results bear out thisprediction

the-Always remember that theories (models) are human inventions They represent tempts to explain observed natural behavior in terms of human experiences A theory isactually an educated guess We must continue to do experiments and to refine our theo-ries (making them consistent with new knowledge) if we hope to approach a more nearlycomplete understanding of nature

at-As scientists observe nature, they often see that the same observation applies to manydifferent systems For example, studies of innumerable chemical changes have shown thatthe total observed mass of the materials involved is the same before and after the change

Such generally observed behavior is formulated into a statement called a natural law For

example, the observation that the total mass of materials is not affected by a chemical

change in those materials is called the law of conservation of mass.

Note the difference between a natural law and a theory A natural law is a summary

of observed (measurable) behavior, whereas a theory is an explanation of behavior A law

summarizes what happens; a theory (model) is an attempt to explain why it happens.

In this section we have described the scientific method as it might ideally be applied(see Fig 1.5) However, it is important to remember that science does not always progresssmoothly and efficiently For one thing, hypotheses and observations are not totally inde-pendent of each other, as we have assumed in the description of the idealized scientific

Experiment Prediction

Observation Hypothesis Prediction

The various parts of the scientific method.

Robert Boyle (1627–1691) was born in Ireland He became especially interested in experiments involving air and developed an air pump with which he produced evacuated cylinders He used these cylinders to show that a feather and a lump of lead fall at the same rate in the absence of air resistance and that sound cannot be produced in a vacuum His most famous experiments involved careful measurements of

the volume of a gas as a function of pressure In his book The Skeptical Chymist, Boyle urged that the

ancient view of elements as mystical substances should be abandoned and that an element should stead be defined as anything that cannot be broken down into simpler substances This conception was

in-an importin-ant step in the development of modern chemistry.

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1.2 The Scientific Method 7

CHEMICAL IMPACT

A Note-able Achievement

Post-it Notes, a product of the 3M Corporation,

revolu-tionized casual written communications and personal

reminders Introduced in the United States in 1980, these

sticky-but-not-too-sticky notes have now found countless

uses in offices, cars, and homes throughout the world

The invention of sticky notes occurred over a period of

about 10 years and involved a great deal of serendipity The

adhesive for Post-it Notes was discovered by Dr Spencer F

Silver of 3M in 1968 Silver found that when an acrylate

polymer material was made in a particular way, it formed

cross-linked microspheres When suspended in a solvent and

sprayed on a sheet of paper, this substance formed a “sparse

monolayer” of adhesive after the solvent evaporated

Scan-ning electron microscope images of the adhesive show that

it has an irregular surface, a little like the surface of a gravel

road In contrast, the adhesive on cellophane tape looks

smooth and uniform, like a superhighway The bumpy

sur-face of Silver’s adhesive caused it to be sticky but not so

sticky to produce permanent adhesion, because the number

of contact points between the binding surfaces was limited

When he invented this adhesive, Silver had no specific

ideas for its use, so he spread the word of his discovery to

his fellow employees at 3M to see if anyone had an

appli-cation for it In addition, over the next several years

devel-opment was carried out to improve the adhesive’s

proper-ties It was not until 1974 that the idea for Post-it Notes

popped up One Sunday Art Fry, a chemical engineer for

3M, was singing in his church choir when he became noyed that the bookmark in his hymnal kept falling out Hethought to himself that it would be nice if the bookmarkwere sticky enough to stay in place but not so sticky that itcouldn’t be moved Luckily, he remembered Silver’s glue—and the Post-it Note was born

an-For the next three years Fry worked to overcome themanufacturing obstacles associated with the product By

1977 enough Post-it Notes were being produced to supply3M’s corporate headquarters, where the employees quicklybecame addicted to their many uses Post-it Notes are nowavailable in 62 colors and 25 shapes

In the years since their introduction, 3M has heard someremarkable stories connected to the use of these notes Forexample, a Post-it Note was applied to the nose of a corpo-rate jet, where it was intended to be read by the plane’s LasVegas ground crew Someone forgot to remove it, however.The note was still on the nose of the plane when it landed

in Minneapolis, having survived a take-off and landing andspeeds of 500 miles per hour at temperatures as low as

56F Stories on the 3M Web site also describe how a

Post-it Note on the front door of a home survived the 140 mileper hour winds of Hurricane Hugo and how a foreign officialaccepted Post-it Notes in lieu of cash when a small bribewas needed to cut through bureaucratic hassles

Post-it Notes have definitely changed the way we municate and remember things

com-method The coupling of observations and hypotheses occurs because once we begin toproceed down a given theoretical path, our hypotheses are unavoidably couched in thelanguage of that theory In other words, we tend to see what we expect to see and oftenfail to notice things that we do not expect Thus the theory we are testing helps us be-cause it focuses our questions However, at the very same time, this focusing process maylimit our ability to see other possible explanations

It is also important to keep in mind that scientists are human They have prejudices;they misinterpret data; they become emotionally attached to their theories and thus loseobjectivity; and they play politics Science is affected by profit motives, budgets, fads,wars, and religious beliefs Galileo, for example, was forced to recant his astronomicalobservations in the face of strong religious resistance Lavoisier, the father of modernchemistry, was beheaded because of his political affiliations Great progress in the chem-istry of nitrogen fertilizers resulted from the desire to produce explosives to fight wars.The progress of science is often affected more by the frailties of humans and theirinstitutions than by the limitations of scientific measuring devices The scientific meth-ods are only as effective as the humans using them They do not automatically lead

to progress

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1.3 Units of Measurement

Making observations is fundamental to all science A quantitative observation, or

mea-surement, always consists of two parts: a number and a scale (called a unit) Both parts

must be present for the measurement to be meaningful

In this textbook we will use measurements of mass, length, time, temperature, tric current, and the amount of a substance, among others Scientists recognized long agothat standard systems of units had to be adopted if measurements were to be useful Ifevery scientist had a different set of units, complete chaos would result Unfortunately,different standards were adopted in different parts of the world The two major systems

elec-are the English system used in the United States and the metric system used by most of

the rest of the industrialized world This duality causes a good deal of trouble; for ple, parts as simple as bolts are not interchangeable between machines built using the twosystems As a result, the United States has begun to adopt the metric system

exam-Most scientists in all countries have for many years used the metric system In 1960,

an international agreement set up a system of units called the International System (le

Système International in French), or the SI system This system is based on the metric

system and units derived from the metric system The fundamental SI units are listed inTable 1.1 We will discuss how to manipulate these units later in this chapter

Because the fundamental units are not always convenient (expressing the mass of apin in kilograms is awkward), prefixes are used to change the size of the unit These arelisted in Table 1.2 Some common objects and their measurements in SI units are listed

in Table 1.3

Soda is commonly sold in 2-liter bottles—

an example of the use of SI units in

every-day life.

CHEMICAL IMPACT

Critical Units!

How important are conversions from one unit to another?

If you ask the National Aeronautics and Space

Admin-istration (NASA), very important! In 1999 NASA lost a $125

million Mars Climate Orbiter because of a failure to convert

from English to metric units

The problem arose because two teams working on the

Mars mission were using different sets of units NASA’s

sci-entists at the Jet Propulsion Laboratory in Pasadena,

Cali-fornia, assumed that the thrust data for the rockets on the

Orbiter they received from Lockheed Martin Astronautics in

Denver, which built the spacecraft, were in metric units In

reality, the units were English As a result the Orbiter dipped

100 kilometers lower into the Mars atmosphere than planned

and the friction from the atmosphere caused the craft to

burn up

NASA’s mistake refueled the controversy over whether

Congress should require the United States to switch to the

metric system About 95% of the world now uses the

met-ric system, and the United States is slowly switching from

English to metric For example, the automobile industry has

adopted metric fasteners and we buy our soda in two-liter

bottles

Units can be very important In fact, they can mean thedifference between life and death on some occasions In 1983,for example, a Canadian jetliner almost ran out of fuel whensomeone pumped 22,300 pounds of fuel into the aircraft in-stead of 22,300 kilograms Remember to watch your units!

Artist’s conception of the lost Mars Climate Orbiter

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1.3 Units of Measurement 9

TABLE 1.1 The Fundamental SI Units

TABLE 1.3 Some Examples of Commonly Used Units

A quarter is 2.5 cm in diameter

The average height of an adult man is 1.8 m.

Mass A nickel has a mass of

about 5 g

A 120-lb person has a mass of about 55 kg.

has a volume of about

360 mL.

TABLE 1.2 The Prefixes Used in the SI System (Those most commonly

encountered are shown in blue.)

The largest cube has sides 1 m in length

and a volume of 1 m 3 The middle-sized

cube has sides 1 dm in length and a

vol-ume of 1 dm 3 , or 1 L The smallest cube

has sides 1 cm in length and a volume of

1 cm 3 , or 1 mL.

One physical quantity that is very important in chemistry is volume, which is not a

fun-damental SI unit but is derived from length A cube that measures 1 meter (m) on each edge

is represented in Fig 1.6 This cube has a volume of (1 m)3 1 m3 Recognizing that thereare 10 decimeters (dm) in a meter, the volume of this cube is (1 m)3 (10 dm)3 1000

dm3 A cubic decimeter, that is (1 dm)3, is commonly called a liter (L), which is a unit of

volume slightly larger than a quart As shown in Fig 1.6, 1000 liters are contained in a cubewith a volume of 1 cubic meter Similarly, since 1 decimeter equals 10 centimeters (cm),the liter can be divided into 1000 cubes each with a volume of 1 cubic centimeter:

Also, since 1 cm3 1 milliliter (mL),

Thus 1 liter contains 1000 cubic centimeters, or 1000 milliliters

Chemical laboratory work frequently requires measurement of the volumes of liquids.Several devices for the accurate determination of liquid volume are shown in Fig 1.7

An important point concerning measurements is the relationship between mass and

weight Although these terms are sometimes used interchangeably, they are not the same.

1 liter 1000 cm3 1000 mL

1 liter 11 dm23 110 cm23 1000 cm3

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Mass is a measure of the resistance of an object to a change in its state of motion Mass

is measured by the force necessary to give an object a certain acceleration On earth weuse the force that gravity exerts on an object to measure its mass We call this force the

object’s weight Since weight is the response of mass to gravity, it varies with the strength

of the gravitational field Therefore, your body mass is the same on the earth or on themoon, but your weight would be much less on the moon than on earth because of themoon’s smaller gravitational field

Because weighing something on a chemical balance (see Fig 1.8) involves

compar-ing the mass of that object to a standard mass, the terms weight and mass are sometimes

used interchangeably, although this is incorrect

1.4 Uncertainty in Measurement

The number associated with a measurement is obtained using some measuring device Forexample, consider the measurement of the volume of a liquid using a buret (shown in Fig 1.9with the scale greatly magnified) Notice that the meniscus of the liquid occurs at about20.15 milliliters This means that about 20.15 mL of liquid has been delivered from the bu-ret (if the initial position of the liquid meniscus was 0.00 mL) Note that we must estimatethe last number of the volume reading by interpolating between the 0.1-mL marks Sincethe last number is estimated, its value may be different if another person makes the samemeasurement If five different people read the same volume, the results might be as follows:

100

mL

0 1 2 3 4

50 49 48 47 46 45 44

Calibration mark indicates 250-mL volume

FIGURE 1.7

Common types of laboratory equipment used to measure liquid volume.

FIGURE 1.8

An electronic analytical balance.

Measurement of volume using a buret The

volume is read at the bottom of the liquid

curve (called the meniscus).

Trang 36

1.4 Uncertainty in Measurement 11

These results show that the first three numbers (20.1) remain the same regardless of who

makes the measurement; these are called certain digits However, the digit to the right of the 1 must be estimated and therefore varies; it is called an uncertain digit We custom- arily report a measurement by recording all the certain digits plus the first uncertain digit.

In our example it would not make any sense to try to record the volume of thousandths

of a milliliter because the value for hundredths of a milliliter must be estimated whenusing the buret

It is very important to realize that a measurement always has some degree of

uncer-tainty The uncertainty of a measurement depends on the precision of the measuring

de-vice For example, using a bathroom scale, you might estimate the mass of a grapefruit

to be approximately 1.5 pounds Weighing the same grapefruit on a highly precise ance might produce a result of 1.476 pounds In the first case, the uncertainty occurs inthe tenths of a pound place; in the second case, the uncertainty occurs in the thousandths

bal-of a pound place Suppose we weigh two similar grapefruits on the two devices and obtainthe following results:

Do the two grapefruits have the same mass? The answer depends on which set of resultsyou consider Thus a conclusion based on a series of measurements depends on the cer-tainty of those measurements For this reason, it is important to indicate the uncertainty

in any measurement This is done by always recording the certain digits and the first

un-certain digit (the estimated number) These numbers are called the significant figures of

Uncertainty in measurement is discussed

in more detail in Appendix 1.5

Sample Exercise 1.1

Trang 37

you should record a reading of twenty-five milliliters as 25.00 mL, not 25 mL This way

at some later time when you are using your results to do calculations, the uncertainty inthe measurement will be known to you

Precision and Accuracy

Two terms often used to describe the reliability of measurements are precision and

accu-racy Although these words are frequently used interchangeably in everyday life, they have

different meanings in the scientific context Accuracy refers to the agreement of a ticular value with the true value Precision refers to the degree of agreement among sev-

par-eral measurements of the same quantity Precision reflects the reproducibility of a given

type of measurement The difference between these terms is illustrated by the results ofthree different dart throws shown in Fig 1.10

Two different types of errors are illustrated in Fig 1.10 A random error (also called

an indeterminate error) means that a measurement has an equal probability of being high

or low This type of error occurs in estimating the value of the last digit of a

measure-ment The second type of error is called systematic error (or determinate error) This

type of error occurs in the same direction each time; it is either always high or alwayslow Figure 1.10(a) indicates large random errors (poor technique) Figure 1.10(b) indi-cates small random errors but a large systematic error, and Figure 1.10(c) indicates smallrandom errors and no systematic error

In quantitative work, precision is often used as an indication of accuracy; we assume

that the average of a series of precise measurements (which should “average out” the

ran-dom errors because of their equal probability of being high or low) is accurate, or close

to the “true” value However, this assumption is valid only if systematic errors are absent.Suppose we weigh a piece of brass five times on a very precise balance and obtain thefollowing results:

The results of several dart throws show the

difference between precise and accurate.

(a) Neither accurate nor precise (large

ran-dom errors) (b) Precise but not accurate

(small random errors, large systematic error).

(c) Bull’s-eye! Both precise and accurate

(small random errors, no systematic error).

surements is an indication of accuracy only if systematic errors are absent.

Precision and Accuracy

To check the accuracy of a graduated cylinder, a student filled the cylinder to the 25-mLmark using water delivered from a buret (see Fig 1.7) and then read the volume deliv-ered Following are the results of five trials:

2.486 g 2.487 g  2.485 g  2.484 g  2.488 g

Trang 38

1.5 Significant Figures and Calculations 13

See Question 1.11.

1.5 Significant Figures and Calculations

Calculating the final result for an experiment usually involves adding, subtracting, plying, or dividing the results of various types of measurements Since it is very impor-tant that the uncertainty in the final result is known correctly, we have developed rules forcounting the significant figures in each number and for determining the correct number

multi-of significant figures in the final result

Rules for Counting Significant Figures

a Leading zeros are zeros that precede all the nonzero digits These do not count as

significant figures In the number 0.0025, the three zeros simply indicate the sition of the decimal point This number has only two significant figures

po-b Captive zeros are zeros between nonzero digits These always count as significant

figures The number 1.008 has four significant figures

c Trailing zeros are zeros at the right end of the number They are significant only if

the number contains a decimal point The number 100 has only one significantfigure, whereas the number 1.00 102has three significant figures The numberone hundred written as 100 also has three significant figures

us-ing measurus-ing devices but were determined by countus-ing: 10 experiments, 3 apples,

8 molecules Such numbers are called exact numbers They can be assumed to have

an infinite number of significant figures Other examples of exact numbers are the

2 in 2␲r (the circumference of a circle) and the 4 and the 3 in (the volume of

a sphere) Exact numbers also can arise from definitions For example, one inch is

defined as exactly 2.54 centimeters Thus, in the statement 1 in 2.54 cm, neitherthe 2.54 nor the 1 limits the number of significant figures when used in a calculation

Note that the number 1.00 102above is written in exponential notation This type

of notation has at least two advantages: the number of significant figures can be easily

4

3pr3

Precision is an indication of accuracy

only if there are no systematic errors

Leading zeros are never significant

figures

Captive zeros are always significant

figures

Exact numbers never limit the number of

significant figures in a calculation

Trailing zeros are sometimes significant

figures

Exponential notation is reviewed in

Appendix 1.1

Trang 39

indicated, and fewer zeros are needed to write a very large or very small number Forexample, the number 0.000060 is much more conveniently represented as 6.0 1025 (Thenumber has two significant figures.)

Significant Figures

Give the number of significant figures for each of the following results

a A student’s extraction procedure on tea yields 0.0105 g of caffeine.

b A chemist records a mass of 0.050080 g in an analysis.

c In an experiment a span of time is determined to be 8.050 103s

Solution

a The number contains three significant figures The zeros to the left of the 1 are

lead-ing zeros and are not significant, but the remainlead-ing zero (a captive zero) is significant

b The number contains five significant figures The leading zeros (to the left of the 5) are

not significant The captive zeros between the 5 and the 8 are significant, and the ing zero to the right of the 8 is significant because the number contains a decimal point

trail-c This number has four significant figures Both zeros are significant.

See Exercises 1.25 through 1.28.

To this point we have learned to count the significant figures in a given number Next,

we must consider how uncertainty accumulates as calculations are carried out The detailedanalysis of the accumulation of uncertainties depends on the type of calculation involvedand can be complex However, in this textbook we will employ the following simple rulesthat have been developed for determining the appropriate number of significant figures inthe result of a calculation

Rules for Significant Figures in Mathematical Operations*

same as the number in the least precise measurement used in the calculation Forexample, consider the calculation

h

Corrected

h

Limiting term has Two significant

figures

The product should have only two significant figures, since 1.4 has two significant figures

least precise measurement used in the calculation For example, consider the sum

12.11 18.0 mLimiting term has one decimal place

1.013

Corrected

31.123 888888n 31.1

h

One decimal place

The correct result is 31.1, since 18.0 has only one decimal place

4.56  1.4  6.38

Sample Exercise 1.3

*Although these simple rules work well for most cases, they can give misleading results in certain cases.

For more information, see L M Schwartz, “Propagation of Significant Figures,” J Chem Ed 62 (1985):

693; and H Bradford Thompson, “Is 8C equal to 50F?” J Chem Ed 68 (1991): 400.

Trang 40

1.5 Significant Figures and Calculations 15

Note that for multiplication and division, significant figures are counted For additionand subtraction, the decimal places are counted

In most calculations you will need to round numbers to obtain the correct number ofsignificant figures The following rules should be applied when rounding

Rules for Rounding

1. In a series of calculations, carry the extra digits through to the final result, then round.

2. If the digit to be removed

a is less than 5, the preceding digit stays the same For example, 1.33 rounds to 1.3

b is equal to or greater than 5, the preceding digit is increased by 1 For example,1.36 rounds to 1.4

Although rounding is generally straightforward, one point requires special emphasis

As an illustration, suppose that the number 4.348 needs to be rounded to two significant

figures In doing this, we look only at the first number to the right of the 3:

4.348h Look at this number to round to two significant figures.

The number is rounded to 4.3 because 4 is less than 5 It is incorrect to round sequentially

For example, do not round the 4 to 5 to give 4.35 and then round the 3 to 4 to give 4.4 When rounding, use only the first number to the right of the last significant figure.

It is important to note that Rule 1 above usually will not be followed in the ple Exercises in this text because we want to show the correct number of significant

Sam-figures in each step of a problem This same practice is followed for the detailed solutions given in the Solutions Guide However, as stated in Rule 1, the best proce-

dure is to carry extra digits throughout a series of calculations and round to the correctnumber of significant figures only at the end This is the practice you should follow.The fact that your rounding procedures are different from those used in this text must

be taken into account when you check your answer with the one given at the end of

the book or in the Solutions Guide Your answer (based on rounding only at the end

of a calculation) may differ in the last place from that given here as the “correct”answer because we have rounded after each step To help you understand the differ-ence between these rounding procedures, we will consider them further in SampleExercise 1.4

Significant Figures in Mathematical Operations

Carry out the following mathematical operations, and give each result with the correctnumber of significant figures

a 1.05 103 6.135

b 21 13.8

c As part of a lab assignment to determine the value of the gas constant (R), a student

measured the pressure (P), volume (V ), and temperature (T ) for a sample of gas, where

The following values were obtained: P  2.560, T  275.15, and V  8.8 (Gases will be

discussed in detail in Chapter 5; we will not be concerned at this time about the units for

these quantities.) Calculate R to the correct number of significant figures.

T

Rule 2 is consistent with the operation of

electronic calculators

Do not round sequentially The number

6.8347 rounded to three significant

figures is 6.83, not 6.84

Sample Exercise 1.4

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