General, Organic and Biological Chemistry: An Integrated Approach, Second Edition [Second Edition] 0470129271, 9780470129272

Citation preview

General, Organic, and Biological Chemistry: An Integrated Approach, Second Edition

Kenneth W. Raymond

John Wiley & Sons, Inc.

Every one of your students has the potential to make a difference. And realizing that potential starts right here, in your course. When students succeed in your course—when they stay on-task and make the breakthrough that turns confusion into confidence—they are empowered to realize the possibilities for greatness that lie within each of them. We know your goal is to create an environment where students reach their full potential and experience the exhilaration of academic success that will last them a lifetime. WileyPLUS can help you reach that goal.

WileyPLUS is a suite of resources—including the complete online text—that will help your students: • come to class better prepared for your lectures • get immediate feedback and context-sensitive help on assignments and quizzes • track their progress throughout the course

www.wileyplus.com

88%

of students surveyed said it improved their understanding of the material. *

TO THE INSTRUCTOR

WileyPLUS is built around the activities you perform Prepare & Present Create outstanding class presentations using a wealth of resources, such as PowerPoint™ slides, image galleries, interactive learningware, and more. Plus you can easily upload any materials you have created into your course, and combine them with the resources Wiley provides you with.

CATALYST With the 2nd edition of Raymond GOB, we are introducing an innovative online learning program called CATALYST. The CATALYST assignments ask students to consider the key concepts and topics at hand from different perspectives; with different givens/desired responses required each time a new question is presented.

Create Assignments

*Based on 7000 survey responses from student users of WileyPLUS in academic year 2006-2007.

Automate the assigning and grading of homework or quizzes by using the provided question banks. Student results will be automatically graded and recorded in your gradebook. WileyPLUS also links homework problems to relevant sections of the online text, hints, or solutions— context-sensitive help where students need it most!

in your class each day. With WileyPLUS you can: Track Student Progress Keep track of your students' progress via an instructor's gradebook, which allows you to analyze individual and overall class results. This gives you an accurate and realistic assessment of your students’ progress and level of understanding.

Now Available with WebCT and eCollege! Now you can seamlessly integrate all of the rich content and resources available with WileyPLUS with the power and convenience of your WebCT or eCollege course. You and your students get the best of both worlds with single sign-on, an integrated gradebook, list of assignments and roster, and more. If your campus is using another course management system, contact your local Wiley Representative.

“I studied more for this class than I would have without WileyPLUS.” Melissa Lawler, Western Washington Univ.

For more information on what WileyPLUS can do to help your students reach their potential, please visit TM

www.wileyplus.com/experience

84%

of students would recommend WileyPLUS to their next instructors.*

TO THE STUDENT

You have the potential to make a difference! WileyPLUS is a powerful online system packed with features to help you make the most of your potential, and get the best grade you can!

With WileyPLUS you get: A complete online version of your text and other study resources Study more effectively and get instant feedback when you practice on your own. Resources like self-assessment quizzes, interactive learningware, and video clips bring the subject matter to life, and help you master the material.

Problem-solving help, instant grading, and feedback on your homework and quizzes You can keep all of your assigned work in one location, making it easy for you to stay on task. Plus, many homework problems contain direct links to the relevant portion of your text to help you deal with problem-solving obstacles at the moment they come up.

74%

The ability to track your progress and grades throughout the term. A personal gradebook allows you to monitor your results from past assignments at any time. You’ll always know exactly where you stand.

If your instructor uses WileyPLUS, you will receive a URL for your class. If not, your instructor can get more information about WileyPLUS by visiting www.wileyplus.com

“It has been a great help, and I believe it has helped me to achieve a better grade.” Michael Morris, Columbia Basin College

of students surveyed said it helped them get a better grade. *

GENERAL, ORGANIC, AND BIOLOGICAL CHEMISTRY

An Integrated Approach SECOND

EDITION

GENERAL, ORGANIC, AND BIOLOGICAL CHEMISTRY

An Integrated Approach SECOND

Kenneth W. Raymond

Eastern Washington University

John Wiley & Sons, Inc.

EDITION

VICE PRESIDENT AND EXECUTIVE PUBLISHER PROJECT EDITOR PRODUCTION SERVICES MANAGER PRODUCTION EDITOR EXECUTIVE MARKETING MANAGER CREATIVE DIRECTOR ART DIRECTOR DESIGNER SENIOR PHOTO EDITOR EDITORIAL ASSISTANT SENIOR MEDIA EDITOR PRODUCTION MANAGEMENT COVER ILLUSTRATION/DESIGN BICENTENNIAL LOGO DESIGN COVER PHOTOS

Kaye Pace Jennifer Yee Dorothy Sinclair Janet Foxman Amanda Wygal Harry Nolan Hope Miller Brian Salisbury Lisa Gee Catherine Donovan Thomas Kulesa Suzanne Ingrao/Ingrao Associates Norm Christiansen Richard J. Pacifico Image of orange based on photo © Stock Food/Punchstock (top) and © Photodisc/Superstock (bottom)

This volume contains selected illustrations from the following texts, reprinted with permission by John Wiley and Sons, Inc. • Boyer, Rodney, Concepts in Biochemistry, Second Edition, © 2002. • Hein, Morris; Best, Leo R.; Pattison, Scott; Arena, Susan, Introduction to General, Organic, and Biochemistry, Eighth Edition, © 2005. • Holum, John R., Fundamentals of General, Organic, and Biological Chemistry, Sixth Edition, © 1998. • Pratt, Charlotte W.; Cornely, Kathleen, Essential Biochemistry, © 2004. • Voet, Donald; Voet, Judith G.; Pratt, Charlotte W., Fundamentals of Biochemistry: Life at the Molecular Level, 2nd Edition, © 2006.

This book was set in 10.5/12 Adobe Garamond by Preparé and printed and bound by Courier/Kendallville. The cover was printed by Courier/Kendallville. This book is printed on acid-free paper. f Copyright © 2008 John Wiley & Sons, Inc. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, website www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030-5774, (201) 748-6011, fax (201) 748-6008, website www.wiley.com/go/permissions. To order books or for customer service, please call 1-800-CALL WILEY (225-5945).

ISBN: 978-0-470-12927-2 Printed in the United States of America 10

9

8

7

6

5

4

3

2

1

P R E F A C E

his second edition of General, Organic, and Biochemistry: an Integrated Approach T has been written for students preparing for careers in health-related fields such as nursing, dental hygiene, nutrition, medical technology, and occupational therapy. The text is also suitable for students majoring in other fields where it is important to have an understanding of chemistry and its relationship to living things. Students need have no previous background in chemistry, but should possess basic math skills. For those whose math is a bit rusty, the text provides reviews of the important material. While designed for use in one-semester or two-quarter General, Organic, and Biochemistry (GOB) courses, instructors have found that it also works well for one-year courses, especially when combined with the supplement Chemistry Case Studies For Allied Health Students by Colleen Kelley and Wendy Weeks. In a GOB course it is essential to show how the subject matter relates to the students’ future careers. For this reason, this text makes extensive use of real-life examples from the health sciences.

O R G A N I Z A T I O N In most GOB texts, a group of chapters on general chemistry is followed by a series of organic chemistry chapters, which is followed by chapters devoted to biochemistry. Years of experience in teaching health science courses have shown the author that there is a drawback to this approach: in many cases there is a long time interval between when a topic is first presented and when it is used again—enough of a break that students’ familiarity with the subject matter has often lapsed. In introducing GOB material, this text uses an integrated approach in which related general chemistry, organic chemistry, and biochemistry topics are presented in adjacent chapters. This approach helps students see the strong connections that exist between these three branches of chemistry and allows instructors to discuss these interrelationships while the material is still fresh in students’ minds. This integration involves the following sets of chapters: • Chapter 3 (Compounds) and Chapter 4 (An Introduction to Organic Compounds). An introduction to bonding and compounds is followed by a look at the members of a few key organic families. • Chapters 3 and 4 and Chapter 6 (Reactions). A study of inorganic and organic compounds is followed (after a look at gases, liquids, and solids in Chapter 5) by an introduction to their reactions. • Chapter 7 (Solutions) and Chapter 8 (Lipids and Membranes). A discussion of solubility is followed by a look at the importance of solubility in biochemistry. Some reactions from Chapter 6 are reintroduced. • Chapter 9 (Acids and Bases) and Chapter 10 (Carboxylic Acids, Phenols, and Amines). Principles of acid/base chemistry from an inorganic perspective are followed by a chapter on the organic and biochemical aspects of this topic.

x

PREFACE

• Chapter 11 (Alcohols, Aldehydes, and Ketones) and Chapter 12 (Carbohydrates). An introduction to the chemistry of alcohols, aldehydes and ketones is followed by a presentation of related biochemical applications. The many reviewers of this text have made helpful suggestions. The major changes to the second edition are:

K E Y F E AT U R E S OF THE SECOND EDITION

• Newly introduced material: Molar mass (Chapter 2), step-by-step instructions for drawing molecules and polyatomic ions (Chapter 4), ionic equations and net ionic equations (Chapter 7), and naming esters and amides (Chapter 10). • Revised material: Changed group naming from IA, IIA format to 1A, 2A format (Chapter 2), added details on naming binary molecules and introduced a table of prefixes used for naming them (Chapter 2), modified treatment of the combined gas law and the ideal gas law (Chapter 5), and updated discussion of waxes, fatty acids, phospholipids, and eicosanoids (Chapter 8). • New Appendicies: Important families of organic compounds (Appendix B) and Naming ions, ionic compounds, binary molecules, and organic compounds (Appendix C). • Addition of new chapter sections: Reaction types (Section 6.2), Maintaining the pH of blood serum (Section 9.10), and Oxidation of phenols (Section 10.5).

P R O B L E M

S O LV I N G Learning to do anything requires practice, and in chemistry this practice involves solving problems. This text offers students ample opportunities to do so.

102

CHAPTER 4 | AN INTRODUCTION

■ FIGURE |

TO

ORGANIC COMPOUNDS

H H H H

4.3 H

(Continued)

C

C

C

CH3CH2CHCH3

C H

H H F

F

H

F

2-Fluorobutane

O H H

C C

C C C

O H C C

O

O H C H

O C

HC

H

HC

H

H

C C C H

OH C

O

O CCH3

O

OH O

CH

O

• Sample Problems and Practice Problems.

Aspirin

In skeletal structures (Figure 4.3), covalent bonds are represented by lines, carbon atoms are not shown, and hydrogen atoms are drawn only when attached to atoms other than carbon. To read a skeletal structure, you assume that a carbon atom appears where lines (bonds) meet and at the end of each line. To simplify matters, nonbonding electrons (Section 3.5) are sometimes omitted from skeletal and other structural formulas. S AMPLE P ROBLEM

4.4

Drawing condensed and skeletal structures Draw condensed and skeletal structures of diethyl ether, a compound once used as a general anesthetic. H H H H ƒ

ƒ

ƒ

ƒ

ƒ

ƒ

ƒ

ƒ

• ¬ C ¬ C ¬H H¬ C ¬ C ¬O ¶ H H

H H

Strategy

To write the condensed formula, begin by thinking of the molecule as a chain of five atoms (C¬ C¬ O¬ C¬ C) and then add in the atoms attached to these five (CH3, etc.). The skeletal structure of diethyl ether is drawn by leaving out all of the carbon and hydrogen atoms, showing only the oxygen atom and the C¬ C and C¬ O bonds. Solution

O

CH3CH2OCH2CH3 Condensed structure

P RACTICE P ROBLEM

Skeletal structure

4.4

Research suggests that drinking green tea may help boost the immune system. Ethylamine (below), produced when one of the compounds in green tea is broken down in the liver, may be responsible for this immune response. Draw condensed and skeletal structures for the molecule. H H ƒ

ƒ

ƒ

ƒ

H¬ C ¬ C ¬ N ¶ ¬H ƒ

H H H

Each major topic is followed by a sample problem and a related practice problem. The solution to each sample problem is accompanied by a strategy to use when solving the problem. The answers to practice problems are given at the end of the chapter.

PREFACE

END

CHAPTER PROBLEMS

OF

131

8 Define the term “functional group” and describe the features

that distinguish hydrocarbons, alcohols, carboxylic acids, and esters from one another. Functional groups are atoms, groups of atoms, or bonds that give a molecule a particular set of chemical properties. The functional groups represented in hydrocarbons are the carbon–carbon double bond (in alkenes), the carbon–carbon triple bond (in alkynes), and alternating double and single bonds in a ring (in aromatic compounds). Alcohols contain the hydroxyl (¬ OH) functional group attached to an alkane-like carbon atom. Carboxylic acids contain the hydroxyl group attached to a carbonyl (C“ O) group, and esters contain a C¬ O¬ C linkage, with one of the carbon atoms belonging to a carbonyl group.

• End of Chapter Problems. A large number of END

OF

CHAPTER

problems can be found and the end of each chapter, and Appendix D provides answers for the odd-numbered ones. Many of the end of chapter problems are paired and some, marked with an asterisk, are more challenging than others. Each chapter includes a set of Thinking It Through problems that ask students to go a bit further with one or more of the concepts presented in the chapter. Over two hundred and fifty new problems have been added to the second edition. Of these, more than half are multi-part questions and many are challenging.

PROBLEMS

Answers to problems whose numbers are printed in color are given in Appendix D. More challenging questions are marked with an asterisk. Problems within colored rules are paired. ILW = Interactive Learning Ware solution is available at www.wiley.com/college/raymond. |

4.1 S T R U C T U R A L F O R M U L A S

AND

FORMAL CHARGES 4.1 Draw the line-bond structure of each molecule.

CH3 a.

HC

C C H

• a. H¬ ¶ S ¬H

C

CH3CH2CHCH2CH3

HC

following molecules or ions?

following molecules or ions? +

H H

4.2 Draw the line-bond structure of each molecule.

CH3 ƒ

S

‘

• ≠O

CH

ƒ

ƒ

•l≠ ≠C

2−

4.10 What is the formal charge on each atom in the

CH

a. CH3CCH2CH3

•l¬N •l≠ c. ≠C ¶ ¶¬ C ¶

•≠ • ¬ C ¬O b. ≠O ¶ ¶

CH2CH2NH2 b.

4.9 What is the formal charge on each atom in the

b. CH3CH“CHCH“CH2

CH3

ƒ

ƒ

ƒ

ƒ

a. D H¬ C ¬N¬H T

•l¬O •≠4− • ¬C ¶ ¶ ¶ c. 3≠O

H H

O ¶≠ ‘

b. H¬ C ¬H 4.11 Draw each polyatomic ion and assign formal charges.

4.3 What is the shape around the nitrogen and sulfur atoms

in the ions shown in Figure 4.2? 4.4 What is the shape around each of the carbon atoms in

aspirin (Figure 4.3)? 4.5 Draw each molecule. a. C2H6 b. C2H4

c. C2H2

4.6 Draw each molecule. a. C3H8 b. C3H6

c. C3H4

4.7 Draw each diatomic element. a. F2 b. O2 c. N2

* 4.8 Draw two different molecules that have the formula C2H6O.

Each atom, except for hydrogen, should have an octet of valence electrons. a. OH⫺ b. NH4⫹ c. CN⫺ 4.12 Draw each polyatomic ion and assign formal charges.

Each atom, except for hydrogen, should have an octet of valence electrons. a. PO43⫺ b. HPO42⫺ c. H2PO4⫺ 4.13 Draw each of the following and assign formal charges.

Each atom should have an octet of valence electrons. a. SO3 b. SO32⫺ 4.14 Draw each molecule and assign formal charges. Each

atom should have an octet of valence electrons. a. CO b. SO2

SOLUTIONS

H E A LT H L i n k | CT and MRI Imaging

2.71 A nurse is assisting a patient who has just undergone

cancer treatment that involved exposure to gamma radiation from cobalt-60. Should the nurse be concerned that he will be exposed to gamma radiation given off by the patient? 2.72 In late 2006, a former Russian spy was poisoned when a small amount of polonium-210 was put in his food. He died a few weeks later. a. Polonium-210 emits alpha particles. Write a balanced nuclear equation for this process. b. This radioisotope has a half-life of 138 days. Of a 2 mg sample, how much would remain after 5 half-lives? c. If alpha particles can be blocked by a sheet of paper (Figure 2.13), why is polonium-210 so poisonous?

2.69 a. One of the two techniques described in this Health

Link is considered “invasive.” What do you suppose is meant by this term? b. To which technique does this term apply? c. In some cases, the images produced by CT and MRI

are quite similar. If given a choice, which would you rather have run?

• Interactive Learning Ware Problems. The text’s

ILW

INTERACTIVE

LEARNING

2.73 How many atoms are contained in: a. 1.0 mol of calcium? b. 7.88 × 10−6 mol of calcium? c. 7.88 g of calcium? d. 5.2 mg of calcium?

SOLUTIONS

0 + a. 20 12Mg ¡ ? + 1β

148 b. 152 67Ho ¡ 65Tb + ? 0 c. 31 14Si ¡ ? + −1β

TO

PRACTICE

2.2 a. atomic number = 8, mass number = 18; b. atomic number = 17, mass number = 37 31 15P

and 28 15P

2.4 10.8 amu 2.5 S 2.6 a. 3.7 × 1023 atoms; b. 4.8 × 10−12 mol 2.7 a. 2.53 g; b. 0.860 g 2.8

209 81Tl

2.9

192 77Ir

¡

2.10 132 days

192 76Os

+ 01β+

PROBLEMS

2.74 Identify the missing product in each nuclear equation. ILW

2.1 a. protons and neutrons; b. protons and electrons; c. protons and neutrons

2.3

59

term) of using radiation to treat cancer?

for arterial plaque. Why is the presence of plaque in arteries a concern? b. What role does the particle similar to HDL play in the technique that is described?

ILW

PRACTICE PROBLEMS

2.70 What are the pros and cons (both long-term and short-

2.68 a. “Cholesterol Marker” describes using MRI to look

website (http://www.wiley.com/college/raymond) features Interactive Learning Ware (ILW), a step-by-step problem solving tutorial program that guides students through selected problems from the book. The ILW problems are representative of those that students frequently find most difficult and they reinforce students’ critical thinking and problem solving skills. An ILW icon identifies each ILW problem in the end-of-chapter question section.

TO

THINKING IT THROUGH

PROBLEMS

xi

xii

PREFACE

H E A LT H L I N K S A N D B I O C H E M I S T R Y 118

CHAPTER 4 | AN INTRODUCTION

TO

L I N K S

To emphasize the importance of chemistry to the health sciences and to living things, each chapter includes Health Links and Biochemistry Links. In the second edition, eight new Health Links have been added: Body Mass Index (Chapter 1), Dental Fillings (Chapter 3), Making Weight (Chapter 5), Saliva (Chapter 7), Omega-3 fatty acids (Chapter 8), Biofilms (Chapter 10), Drugs in the environment (Chapter 11), and RNA Interference (Chapter 14). In addition, six Health Links from the first edition have been updated: Body Temperature (Chapter 1), Dietary Reference Intakes (formerly Recommended Daily Allowances) (Chapter 2), CT and MRI (formerly CT and PET) (Chapter 2), Sunscreens (Chapter 4), Trans fats (Chapter 8), and Proteins in Medicine (formerly Enzymes in Medicine) (Chapter 13).

ORGANIC COMPOUNDS

Prion Diseases

T

he conformation, or shape, that a molecule takes can greatly influence its biological action. This point is well illustrated by a particular class of proteins, called prions, that have been identified as the cause of mad cow disease (in cattle), scrapie (in sheep), chronic wasting disease (in deer and elk), and new variant Creutzfeldt-Jakob disease, or vCJD (in humans). Proteins are very large molecules formed from amino acid building blocks. Each protein has a favored conformation— some with the protein chain twisted into spirals and bends and some with the chain zigzagged back and forth in a compact form. Prions, short for proteinaceous infection particles, are a type of protein found in the membranes of nerve cells. The prion diseases mentioned above are caused 128 when theC H A P T E R 4 | A N I N T R O D U C T I O N T O O R G A N I C C O M P O U N D S normal prion conformation (PrPc) is twisted into an abnormal shape (PrPsc) (Figure 4.14). When PrPsc comes into contact with PrPc, the PrPc proteins change conformation and become PrPsc. As PrPsc accumulates in affecNormal Prion Protein (PrPc) Disease-Causing Prion (PrPsc) ted animals or humans, sponge-like holes form in the brain, causing dizziness, seizuOdor and Flavor res, and death. ■ FIGURE | 4.14 Prion diseases can be transferred from one he senses of smell and taste depend on specific receptors located in the nose and in the mouth, respectively. We detect an odor or species to another. Cattle are known to get Prions flavor when a compound attaches to these receptors and triggers nerve responses. How the compound interacts with a given recepmad cow disease when fed parts of scrapie(a) The prion protein (PrPc) in its normal conformation. (b) The prion in its tor been determines the particular odor or flavor that it has. In 2004, the Nobel Prize in Physiology or Medicine was awarded to two infected sheep, and vCJD in humans has incorrectly folded (PrPsc) form. researchers who study the biochemistry of the sense of smell. linked to eating mad cow–infected beef. Source: Fred E. Cohen, M.D., D. Phil and Cedric Govaerts, Ph.D., Department of The odor and flavor of fruits is often due to a mixture of esters. The structure of a particular ester determines how it fits a given Cellular & Molecular Pharmacology, University of California San Francisco (UCSF). receptor, so esters containing a different number of carbon atoms are associated with different odors and flavors. For example, the “pineapple” and “apricot” esters differ by three CH2 groups (Figure 4.24). Constitutional isomers can also have different odors and flavors, as is the case for the “apple-like” and “banana” esters, each of which has the molecular formula C7H14O2.

T

4.7

CYCLOALKANES

O In some alkanes, called cycloalkanes, carbon atoms are joined into rings (Figure 4.15). Like CH3CH2CH2C OCH2CH3 their noncyclic counterparts, cycloalkanes are nonpolar molecules that are attracted to one Pineapple another by London forces. To simplify matters, cycloalkanes are usually drawn using skeletal structures, although side views can be useful when considering the orientation of O substituents attached to a ring. When naming cycloalkanes, the ring is usually designated as the parent, which CH is 3CH2CH2C OCH2CH2CH2CH2CH3 named by combining “cyclo” with the appropriate numbering prefix (Table 4.5) and Apricot “ane.” When only one alkyl group is attached to a cycloalkane parent, the carbon atom O that holds that group is carbon 1 (Figure 4.16a), but the number is not included in the name. When a ring holds more than one alkyl group, the ring is numbered from the position and in the direction that gives the lowest numbers. Figure 4.16b shows how this CH3CH2CH2CH2C OCH2CH3 Apple-like

works for the three dimethylcyclopentane constitutional isomers.

The limited rotation of the carbon–carbon single bonds in cycloalkanes has an interesting side effect in that it allows for the existence of stereoisomers, molecules that • have the same molecular formula • have the same atomic connections • have different three-dimensional shapes • are interchanged only by breaking bonds

Orange

O

CH3C

Rose

O

OCH2CH2CHCH3

Peach

CH3

O

Banana

CH2C OCH2CH3

O CH3CH2C

Honey

OCH2CHCH3 CH3

O

Rum

C OCH3

O H

OCH2

CH3CH2CH2C

CH3C OCH2

O

Geometric Isomers

O

CH3C OCH2CH2CH2CH2CH2CH2CH2CH3

C

H2N OCH2CHCH3 CH3 Raspberry

■ FIGURE |

O N - L I N E 124

CHAPTER 4 | AN INTRODUCTION

P RACTICE P ROBLEM

TO

ORGANIC COMPOUNDS

Designate each of the carbon–carbon double bonds in bombykol, a moth pheromone, as cis or trans. H

H C

C

H C C

H

CH2CH2CH2CH2CH2CH2CH2CH2CH2OH Bombykol

Sunscreens

I

CH3O

n addition to the visible light that is present in sunlight, a higher energy form of electromagnetic radiation called ultraviolet (UV) is also found. It is this UV radiation that makes spending too much time in the sun hazardous to your health. UV radiation is divided into three categories (arranged in order of increasing energy) UV-A, UV-B, and UV-C. Although all forms of UV radiation can be harmful, UV-C is the most damaging. We do not usually worry about exposure to UV-C from sunlight, however, because most is screened out by atmospheric ozone. The UV-A and UV-B in sunlight are not blocked by the atmosphere and it is exposure to UV-B that causes sunburns. This form of radiation has also been identified as one of the causes of skin cancer. While UV-A was once thought to be relatively harmless, there is now strong evidence that links wrinkles, other skin damage, and skin cancer to UV-A exposure. To some extent, your skin can protect itself from UV radiation. When sunlight hits the skin, a particular type of cells produce melanin, a black pigment that absorbs UV radiation. A suntan is the result of melanin production. Sunscreens can also provide some degree of protection from the sun. These contain aromatic compounds that block UV-A and UV-B light (Figure 4.22). Not all aromatic compounds are suitable for use as sunscreens—many do not absorb UV, and many are toxic. The SPF (sun protection factor) H O listed on the label of a sunscreen indicates how effective it is at C C Octyl blocking UV radiation. An SPF of C OCH2CHCH2CH2CH2CH3 methoxycinnamate 25 means that it takes 25 times H CH2CH3 longer to get sunburned with the sunscreen applied than without.

O

O

CCH2C

Avobenzone

CH3O CH2SO3H H3C H3C

H

O

C

C

O

CH3 Ecamsule

H

CH3 CH2SO3H

■ FIGURE |

4.22

UV-B and UV-A absorbing compounds in sunscreens

C(CH3)3

Grape Esters

Many esters have pleasing odors and flavors.

V I D E O S

4.11

CH3CH2CH2

4.24

Octyl methoxycinnamate is the UV-B blocker most commonly used in sunscreens. Avobenzone and Ecamsule are UV-A blockers. Ecamsule, which was recently approved for use in the United States, has been a sunscreen ingredient in Canada and Europe since 1993.

For one topic in each chapter, a special icon is used to indicate that an on-line ScienCentral article and video clip are available for viewing. These articles and video clips are of interest because they show how the chemistry being presented pertains to current events. Each set of end of chapter problems includes some related to the video content. The video titles include: Pork on the Run (Chapter 1), Cholesterol Marker (Chapter 2), Glowing Fish (Chapter 3), Tanning & Health (Chapter 4), Breath Of Life (Chapter 5), Hydrogen Cars (Chapter 6), Kidney Bones (Chapter 7), Teen Steroids (Chapter 8), Cystic Fibrosis Mucus (Chapter 9), Meth and the Brain (Chapter 10), Toxin Eaters (Chapter 11), Sweet Spot (Chapter 12), Young Hearts (Chapter 13), Cancer Screening (Chapter 14), Exercise Gene (Chapter 15).

PREFACE

O T H E R

T E X T

xiii

F E A T U R E S Chapter Opening Vignettes Each chapter begins with a story that focuses on the connection between chemistry and high-interest, everyday topics that students can relate to.

Macular degeneration is a disease of the eye with symptoms that include loss of color vision and distortion, blurring, or complete loss of central vision. Peripheral vision is usually unaffected. People with this disease usually have

4

A

N

I N T R O D U C T I O N T O O R G A N I C C O M P O U N D S

Objectives Each chapter begins with a list of goals for the student to achieve. These objectives identify key concepts within each chapter. A summary of how these objectives were met appears at the end of each chapter.

trouble when it comes to reading or recognizing faces. There are a number of factors

that

increase

the

risk

of

getting

macular

degeneration,

including

advanced age, a history of smoking, and diabetes. Stargardt’s disease, an inherited form of macular degeneration that usually

Now that we have seen the basics of how atoms (Chapter 2) and compounds (Chapter 3) are put together, it is time to set the stage for the organic and biochem-

appears before age 30, results from damage to the retina caused by a mal-

istry topics that we will encounter as we move through the text. This chapter will

function in the recycling of an organic molecule essential to the visual process.

begin with an introduction to a range of diverse topics, all of which relate to how bonding patterns, the distribution of electrons, and the shape of a molecule influence the way that it interacts with others. In later sections of the chapter we will apply our knowledge of these interactions to understand the properties of a number of different families of organic compounds (contain carbon atoms). The shape that a molecule has and its interactions with others are important in determining its biological effects. Diseases ranging from Stargardt’s disease (mentioned on the facing page) to mad cow disease (Health Link: Prion Diseases) are directly related to these properties.

Photo source:

92

Science VU/NIH/Visual Unlimited.

objectives After completing this chapter, you should be able to: 1 Draw molecules and polyatomic ions using electron dot and line-bond structures.

Assign formal charges. 2 Describe how condensed structural formulas and skeletal structures differ from

electron dot and line-bond structures. 3 Define electronegativity and explain its relationship to polar covalent bonds. Give a

simple rule that can be used to predict whether or not a covalent bond is polar. 4 List the five basic shapes about an atom in a molecule and describe the rules used

to predict shape. Explain how shape plays a role in determining overall polarity. 5 Describe the noncovalent interactions that attract one compound to another. 6 Describe the four families of hydrocarbons. 7 Explain the difference between constitutional isomers, conformations, and the

stereoisomers known as geometric isomers. Give examples of two different families of hydrocarbons that can exist as geometric isomers. 8 Define the term functional group and describe the features that distinguish

hydrocarbons, alcohols, carboxylic acids, and esters from one another. 93

Student Web Site Within each chapter you will find an icon a indicating that there is a ScienCentral news video at the website with a news story related to chapter content. The web site also features practice quizzes and Interactive Learningware problems. Student Solutions Manual and Study Guide Written by Byron Howell, Tyler Junior College and Adeliza Flores, of Las Positas College, this supplement contains worked out solutions to the odd-numbered text problems; chapter summaries; sample problems, and practice problems. Laboratory Manual Written by David Macaulay, Joseph Bauer, and Molly Bloomfield. This lab manual is written for the one or two-term chemistry lab course for students in the allied health sciences and related fields. These experiments are presented in an integrated table of contents and contain chapter references from General, Organic, and Biological Chemistry: An Integrated Approach, Second Edition. Chemistry Case Studies For Allied Health Students Written by Colleen Kelley and Wendy Weeks. This manual was designed to bring relevance and critical thinking skills to the allied health chemistry course. Students are encouraged to become “diagnosticians” and apply their newly-acquired chemistry knowledge to solving real life health and environmental cases. The case manual also encourages a holistic approach by asking students to synthesize information across topics.

SUPPORT PACKAGE FOR STUDENTS

xiv

PREFACE

SUPPORT PA C K A G E F O R INSTRUCTORS

PowerPoint Lecture Slides Created by Colleen Kelley, Pima Community College, these slides contain lecture outlines and key topics from each chapter of the text, along with supporting artwork and figures from the text. The slides also contain assessment questions and questions for in-class discussion. WileyPlus Homework Management System WileyPlus is a powerful on-line tool that provides a completely integrated suite of teaching and learning resources in one easyto-use web site. WileyPlus integrates Wiley’s world-renowned content with media, including a multimedia version of the text, PowerPoint slides, on-line assessment, and more. Digital Image Archive The text web site includes downloadable files of text images in JPEG format. Test Bank Written by John Singer, Jackson Community College, the test bank includes multiple choice, true/false, and short answer questions. Computerized Test Bank The IBM and Macintosh compatible version of the entire Test Bank has full editing features to help the instructor customize tests. Instructor’s Manual Written by Colleen Kelley, Pima Community College, this supplement provides Chapter Summaries and lecture outlines. Instructor’s Solutions Manual Written by Adeliza Flores, of Las Positas College, this supplement contains worked-out solutions to all of the end-of-chapter problems.

A C K N O W L E D G M E N T S

I wish to thank my wife Susan and my son William for their encouragement, support, and patience. It is with great appreciation that I acknowledge the important contributions made by Jennifer Yee, Catherine Donovan, Suzanne Ingrao, Janet Foxman, Lisa Gee, Hope Miller, Thomas Kulesa, Gabriel Dillon, Amanda Wygal, and all of the others at Wiley who were involved in helping to prepare this second edition. Finally, I wish to acknowledge the important contributions made by the following reviewers of this text: Jeannie Collins University of Southern Indiana

Shaun Schmidt Washburn University

Lynette Rushton South Puget Sound Community College

Myriam Cotton Pacific Lutheran University

John Singer Jackson Community College

Sean Schmidt Washburn University

Stephen Dunham Moravian College

Carnetta Skipworth Bowling Green Community College

Sara Selfe Edmonds Community College

Joseph Fassler Santa Rosa Junior College

Steven Stefanides Wenatchee Valley College

Anna Sequeira Forsyth Tech Community College

Louis Giacinti Milwaukee Area Technical College

Maria Vogt Bloomfield College

Sonja Siewert West Shore Community College

Christina Goode California State University, Fullerton

William Wagener West Liberty State College

Carnetta Skipworth Western Kentucky University

Saifunnissa B. Hassam Santa Rosa Junior College

Wendy Weeks Pima Community College

Robert St. Amand Union County College

Colleen Kelley Pima Community College

Lynda Peebles Texas Woman’s University

Richard Tarkka University of Central Arkansas

Ira Krull Northeastern University

Jennifer Powers Kennesaw State University

Thottumkara Vinod Western Illinois University

Paul Moggach Georgian College

Parris Powers Volunteer State Community College

Tracy Whitehead Henderson State University

Michael Myers California State University, Long Beach

Rita Rhodes University of Tulsa

Todd Wimpfheimer Salem State College

Lynette Rushton South Puget Sound Community College

Lenore Rodicio Miami-Dade College

xv

This page intentionally left blank

A B O U T T H E A U T H O R

Ken Raymond received a B.S. in Chemistry from Central Washington

University in 1975 and a Ph.D. in Organic Chemistry from the University of Washington in 1981. Since joining the faculty of Eastern Washington University in 1982, his primary teaching responsibilities have been in the general, organic, and biochemistry series for the health sciences and in the upper-division organic chemistry lecture and laboratory series. In 1990 he received EWU’s annual award for excellence in teaching. He has been chair of the Department of Chemistry and Biochemistry since 2000. When not grading papers, he plays mandolin and button accordion in a local folk band.

xvii

B R I E F C O N T E N T S

CHAPTER 1

SCIENCE

CHAPTER 2

AT O M S

CHAPTER 3

C O M P O U N D S 60

CHAPTER 4

AN INTRODUCTION C O M P O U N D S 92

CHAPTER 5

GASES, LIQUIDS,

* *

CHAPTER 6

R E A C T I O N S 176

CHAPTER 7

SOLUTIONS, COLLOIDS, S U S P E N S I O N S 212

* *

CHAPTER 8

LIPIDS

CHAPTER 9

ACIDS, BASES, E Q U I L I B R I U M 286

*

CHAPTER 10

CARBOXYLIC ACIDS, PHENOLS, A M I N E S 320

*

CHAPTER 11

ALCOHOLS, ETHERS, ALDEHYDES, A N D K E T O N E S 360

*

CHAPTER 12

C A R B O H Y D R AT E S 396

CHAPTER 13

PEPTIDES, PROTEINS, E N Z Y M E S 432

CHAPTER 14

N U C L E I C A C I D S 468

CHAPTER 15

M E TA B O L I S M 504

The asterisks are color coded to indicate which chapters are integrated.

* *

xviii

AND

AND

AND

MEASUREMENTS 1

E L E M E N T S 26

TO

AND

ORGANIC

S O L I D S 138

AND

M E M B R A N E S 252 AND

AND

AND

C O N T E N T S

CHAPTER

1.1

1

SCIENCE

The Scientific Method

AND

MEASUREMENTS

2

H EALTH Link Science and Medicine

4

1.2

Matter and Energy

1.3

Units of Measurement

1.4

Scientific Notation and Metric Prefixes

9

1.5

Measurements and Significant Figures

11

4 6

H EALTH Link Body Mass Index 1.6

13

Conversion Factors and the Factor Label Method

H EALTH Link Body Temperature CHAPTER

2

2.1

Atoms

2.2

Elements

ATOMS

ELEMENTS

AND

29

Atomic Number and Mass Number

2.4

Periodic Table

2.5

The Mole

2.6

Radioactive Isotopes

2.7

Radioisotopes in Medicine

31

32

34

37 40 43

H EALTH Link CT and MRI Imaging Fission and Fusion

3

49

50

COMPOUNDS

3.1

Ions

3.2

The Arrangement of Electrons

65

B IOCHEMISTRY Link Bioluminescence

70

3.3

60

62

The Octet Rule

71

B IOCHEMISTRY Link Ionophores and Biological Ion Transport 3.4

Ionic Compounds

3.5

Covalent Bonds

3.6

Molecules

73

74 77

78

H EALTH Link Dental Fillings 3.7

26

28

2.3

CHAPTER

15

16

H EALTH Link Dietary Reference Intakes (DRIs)

2.8

1

80

Formula Weight, Molecular Weight, and Molar Mass

B IOCHEMISTRY Link Ethylene, a Plant Hormone

84

81 xix

xx

CONTENTS

4

CHAPTER

AN INTRODUCTION COMPOUNDS 92

4.1

Structural Formulas and Formal Charges

4.2

Polar Covalent Bonds, Shape, and Polarity

4.3

Noncovalent Interactions

4.4

Alkanes

4.5

Constitutional Isomers

4.6

Conformations

94 103

108

110 115

117

H EALTH Link Prion Diseases

118

4.7

Cycloalkanes

4.8

Alkenes, Alkynes, and Aromatic Compounds

118

H EALTH Link Sunscreens 4.9

B IOCHEMISTRY Link Odor and Flavor 5

125

128

GASES, LIQUIDS,

5.1

States of Matter and Energy

5.2

Gases and Pressure The Gas Laws

5.4

Partial Pressure

5.5

Liquids

AND

SOLIDS

140

146

H EALTH Link Blood Pressure 5.3

120

124

Alcohols, Carboxylic Acids, and Esters

CHAPTER

ORGANIC

TO

150

150 158

161

H EALTH Link Making Weight 164 H EALTH Link Breathing 166 5.6

Solids

CHAPTER

167

6

REACTIONS

6.1

Chemical Equations

6.2

Reaction Types

6.3

Oxidation and Reduction

176

178

182 183

H EALTH Link Antiseptics and Oxidation

187

6.4

Reactions Involving Water

6.5

Mole and Mass Relationships in Reactions

6.6

Calculating the Yield of a Reaction

6.7

Free Energy and Reaction Rate

H EALTH Link Carbonic Anhydrase CHAPTER

7

189

198

201

SOLUTIONS, COLLOIDS, SUSPENSIONS 212

7.1

Solutions

7.2

Reactions of Ions in Aqueous Solutions

Hard Water

191

195

214 220

7.3

Solubility of Gases in Water

7.4

Organic Compounds

221

222

H EALTH Link Hyperbaric Medicine

222

216

AND

138

CONTENTS

7.5

Biochemical Compounds

224

H EALTH Link Prodrugs

227 228

7.6

Concentration

7.7

Dilution

7.8

Colloids and Suspensions

236

H EALTH Link Saliva 7.9

237

239

Diffusion and Osmosis

240

H EALTH Link Diffusion and the Kidneys CHAPTER

8.1

8

LIPIDS

Fatty Acids

242

MEMBRANES

AND

252

254

H EALTH Link Omega-3 fatty acids 8.2

Waxes

8.3

Triglycerides

257

258 259

H EALTH Link Trans Fats 265 H EALTH Link Olestra 266 8.4

Phospholipids and Glycolipids

8.5

Steroids

8.6

Eicosanoids

270 272

H EALTH Link Anabolic Steroids 8.7

Membranes

CHAPTER

266

275

275

9

ACIDS, BASES, AND EQUILIBRIUM

9.1

Acids and Bases

9.2

Brønsted–Lowry Acids and Bases

9.3

Equilibrium

9.4

Le Châtelier’s Principle

286

288 289

290 293

B IOCHEMISTRY Link Diving Mammals, Oxygen, and Myoglobin 9.5

Ionization of Water

9.6

The pH Scale

295

296

297

Math Support–Logs and Antilogs 300 B IOCHEMISTRY Link Plants as pH Indicators

301

9.7

Acid and Base Strength

9.8

Neutralizing Acids and Bases

9.9

Effect of pH On Acid and Conjugate Base Concentrations

9.10 Buffers

301 303

9.11 Maintaining the pH of Blood Serum CHAPTER

10

308

CARBOXYLIC ACIDS, PHENOLS, AND AMINES 320

10.1 Carboxylic Acids 10.2 Phenols

305

306

323

324

H EALTH Link A Chili Pepper Painkiller

325

10.3 Carboxylic Acids and Phenols As Weak Organic Acids 10.4 Other Reactions of Carboxylic Acids

329

326

xxi

xxii

CONTENTS

10.5 Oxidation of Phenols 10.6 Amines

332

333

10.7 Amines As Weak Organic Bases 10.8 Amides

336

337

H EALTH Link Biofilms 339 B IOCHEMISTRY Link A Cure for Fleas 10.9 Stereoisomers

340

341

H EALTH Link Adrenaline and Related Compounds CHAPTER

11

346

ALCOHOLS, ETHERS, ALDEHYDES, AND KETONES 360

11.1 Alcohols, Ethers, and Related Compounds 11.2 Preparation

363

367

11.3 Reactions

370

11.4 Aldehydes and Ketones 11.5 Oxidation of Aldehydes

373 374

H EALTH Link Aldehyde Dehydrogenase

376

11.6 Reduction of Aldehydes and Ketones

H EALTH Link Protective Enzymes

376

378

11.7 Reactions of Alcohols with Aldehydes and Ketones

H EALTH Link Drugs in the Environment CHAPTER

12

382

C A R B O H Y D R AT E S

12.1 Monosaccharides

404

12.3 Monosaccharides in Their Cyclic Form 12.4 Oligosaccharides

417

418

H EALTH Link Blood Type 13

406

410

H EALTH Link Relative Sweetness 415 H EALTH Link Indigestible Oligosaccharides

CHAPTER

396

398

12.2 Reactions of Monosaccharides

12.5 Polysaccharides

422

PEPTIDES, PROTEINS, ENZYMES 432

13.1 Amino Acids

379

AND

434

13.2 The Peptide Bond

437

13.3 Peptides, Proteins, and pH 13.4 Protein Structure

440

441

B IOCHEMISTRY Link Collagen and a-Keratin, Two Fibrous Proteins B IOCHEMISTRY Link Hemoglobin, a Globular Protein 448 13.5 Denaturation 13.6 Enzymes

449

449

13.7 Control of Enzyme-Catalyzed Reactions

H EALTH Link Proteins in Medicine

459

453

447

CONTENTS

14

CHAPTER

NUCLEIC ACIDS

468

14.1

Nucleic Acid Building Blocks

14.2

Nucleoside di-and Triphosphates, Cyclic Nucleotides

14.3

Polynucleotides

476

14.4

DNA Structure

477

14.5

Denaturation

14.6

Nucleic Acids and Information Flow

14.7

DNA Replication

14.8

RNA

14.9

Translation

470 475

480 481

482

484 487

H EALTH Link Viruses

489 14.10 Control of Gene Expression

489

H EALTH Link RNA Interference 14.11 Mutation

491

491

H EALTH Link Breast Cancer Genes 14.12 Recombinant DNA

492

492

B IOCHEMISTRY Link DNA Fingerprinting CHAPTER

15

M E TA B O L I S M

494 504

15.1

Metabolic Pathways, Energy, and Coupled Reactions

15.2

Overview of Metabolism

507

B IOCHEMISTRY Link The Origin of Mitochondria

512

15.3

Digestion

512

15.4

Glycolysis

514

15.5

Gluconeogenesis

15.6

Glycogen Metabolism

15.7

Citric Acid Cycle

15.8

Electron Transport Chain and Oxidative Phosphorylation

H EALTH Link Brown Fat 15.9

Lipid Metabolism

519 521

522 524

527 528

15.10 Amino Acid Metabolism

Appendix A

506

Scientific Calculators

532

A-1

Appendix B

Important Families of Organic Compounds

Appendix C

Naming Ions, Ionic Compounds, Binary Molecules, and Organic Compound A-8

Appendix D

Answers to Odd-Numbered Problems

Appendix E

Glossary

Index

I-1

A-51

A-5

A-23

xxiii

This page intentionally left blank

GENERAL, ORGANIC, AND BIOLOGICAL CHEMISTRY

An Integrated Approach SECOND

EDITION

After their first chemistry lecture

a group of students walks

across campus together. One student says, “I want to be a nurse. I can see how we might need to study chemistry, but why does the textbook have to start with a chapter on math? What does math have to do with the health sciences?” The rest of the group voices their agreement. A nursing student walking past the group in the other direction overhears this comment and smiles. “They have no idea how much math they will use,” she thinks to herself.

Photo source:

Rick Madonik/Toronto Star/Zuma Press.

1

S

C I E N C E A N D M E A S U R E M E N T S

In this first chapter of the text we will take a look at science, chemistry, and mathematics, and will see the important role that each plays in the health sciences.

objectives After completing this chapter, you should be able to: 1 Explain the terms scientific method, law, theory, hypothesis, and experiment. 2 Define the terms matter and energy. Describe the three states of matter and the two

forms of energy. 3 Describe and give examples of physical properties and physical change. 4 Convert from one unit of measurement into another. 5 Express values using scientific notation and metric prefixes. 6 Explain the difference between the terms accurate and precise. 7 Use the correct number of significant figures to report the results of calculations

involving measured quantities.

1

CHAPTER 1 | SCIENCE AND MEASUREMENTS

2

1.1

■

THE

SCIENTIFIC

Experiments test hypotheses.

(a)

(b) ■ FIGURE |

1.1

Medical imaging

(a) The first x ray of the human body was taken in 1895 by Wilhelm Roentgen, the discoverer of x rays. In this x ray, you can see the bones of his wife’s hand and her wedding ring. (b) With the improvements that have been made to x-ray equipment, clinicians can now obtain sharper and more detailed images, as in this scan of a patient’s vertebrae. (a) SPL/Photoresearchers; (b) Gondelon/Photo Researchers, Inc.

Source:

METHOD

Science is an approach that is used to try to make sense out of how the universe operates, ranging in scale from the very large (understanding how stars form) to the very small (understanding the behavior of the tiny particles from which everything is made). The knowledge gained from scientific studies has impacted our lives in many positive ways, including our ever-improving ability to treat diseases. For example, the medical scanners (including CT and MRI) and many of the therapeutic drugs (including antibiotics and anti-cancer drugs) used today are available as a result of the careful work of scientists (Figure 1.1). In doing science, the scientific method is the process used to gather and interpret information. Observation is part of this process. One well-known story regarding the importance of observation involves the English scientist Isaac Newton (1642–1727). Reportedly, seeing an apple fall out of a tree led him to formulate the law of gravity, which states that there is an attractive force between any two objects (in this case, between the earth and an apple). This and other scientific laws are statements that describe things that are consistently and reproducibly observed. While a law does not explain why things happen, it can be used to predict what might happen in the future. For example, the law of gravity does not explain why things fall, but it does allow you to predict what will happen if you jump off of a ladder. Explaining observations is a key component of the scientific method. The process begins with the construction of a hypothesis, a tentative explanation (educated guess) that is based on presently known facts. Clinicians, for example, make educated guesses when treating patients. If a patient complains of stomach pains, the clinician will ask a few questions and make a few observations before coming up with a hypothesis (diagnosis) as to the nature of the problem. This hypothesis is based on knowledge of symptoms and diseases. The most important part of the scientific method is what happens once a hypothesis has been constructed—it must be tested by doing careful experiments. To test a hypothesis, a clinician might call for a series of medical tests (