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The most widely used analytical chemistry textbook in the world, Dan Harris's Quantitative Chemical Analysis provides a sound physical understanding of the principles of analytical chemistry, showing how these principles are applied in chemistry and related disciplines—especially in life sciences and environmental science. As always, the new edition incorporates real data, spreadsheets, and a wealth of applications, in a witty, personable presentation that engages students without compromising the depth necessary for a thorough and practical understanding of analytical chemistry.
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“The Experiment” by Sempé © C. Charillon, Paris
QUANTITATIVE CHEMICAL ANALYSIS
Publisher: Clancy Marshall Senior Acquisitions Editor: Jessica Fiorillo Marketing Manager: John Britch Media Editor: Dave Quinn Editorial Assistant: Kristina Treadway Photo Editor: Ted Szczepanski Cover and Text Designer: Vicki Tomaselli Senior Project Editor: Mary Louise Byrd Illustrations: Network Graphics, Precision Graphics Illustration Coordinators: Bill Page, Eleanor Jaekel Production Coordinator: Julia DeRosa Composition and Text Layout: Aptara, Inc. Printing and Binding: RR Donnelley
Library of Congress Control Number: 2009943186 ISBN-13: 978-1-4292-1815-3 ISBN-10: 1-4292-1815-0 © 2010, 2007, 2003, 1999 by W. H. Freeman and Company All rights reserved Printed in the United States of America First Printing W. H. Freeman and Company 41 Madison Avenue New York, NY 10010 Houndmills, Basingstoke RG21 6XS, England www.whfreeman.com
QUANTITATIVE CHEMICAL ANALYSIS Eighth Edition
Daniel C. Harris Michelson Laboratory China Lake, California
W. H. Freeman and Company New York
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BRIEF CONTENTS 0 The Analytical Process
1
1 Chemical Measurements
13
2 Tools of the Trade
29
3 Experimental Error
51
4 Statistics
68
5 Quality Assurance and Calibration Methods 6
Chemical Equilibrium
96 117
7 Activity and the Systematic Treatment of Equilibrium
142
8 Monoprotic Acid-Base Equilibria
162
9 Polyprotic Acid-Base Equilibria
185
10 Acid-Base Titrations
205
11 EDTA Titrations
236
12 Advanced Topics in Equilibrium
258
13 Fundamentals of Electrochemistry 279
18 Applications of Spectrophotometry
419
19 Spectrophotometers
445
20 Atomic Spectroscopy
479
21 Mass Spectrometry
502
22 Introduction to Analytical Separations
537
23 Gas Chromatography
565
24 High-Performance Liquid Chromatography
595
25 Chromatographic Methods and Capillary Electrophoresis
634
26 Gravimetric Analysis, Precipitation Titrations, and Combustion Analysis
673
27 Sample Preparation
699
Notes and References NR1
14 Electrodes and Potentiometry
308
Glossary GL1
15 Redox Titrations
340
Appendixes AP1
16 Electroanalytical Techniques
361
Solutions to Exercises S1
17 Fundamentals of Spectrophotometry
Answers to Problems AN1 393
Index I1
v
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CONTENTS Preface 0
The Analytical Process
1
3-5 Propagation of Uncertainty from Systematic Error
The “Most Important” Environmental Data Set of the Twentieth Century
1
4
0-1 Charles David Keeling and the Measurement of Atmospheric CO2 0-2 The Analytical Chemist’s Job 0-3 General Steps in a Chemical Analysis
1 6 11
Box 0-1 Constructin