Quantitative Chemical Analysis

998 Pages·2015·31.146 MB·English

by  Daniel C. Harris

1
Periodic Table
1 +1
20 H
14
¤
0.0888
Hydrogen 2 Atomic Number
26 +2,3
1.007 98 ±14
Boiling point (K) Common oxidation states
3 +1 4 +2 3135 Fe
Melting point (K) 1809
1615 Li 2745 Be
Atomic mass with uncertainty in last digit
454 1560 7.86 Example: Fe = 55.845 ± 0.002
Density at 300 K
0.53 1.85 (g /cm3 ) Iron Uncertainty in last digit is ±1
Lithium Beryllium
6.968 ±30 9.012 182 ±3 (Densitiesmarked 55.845 ±2 if no uncertainty is indicated
with¤areat273K Numbers in parentheses are
11 +1 12 +2 and1barandthe longest-lived isotope
unitsare g/L)
1156 Na 1363 Mg
Atomic masses from
371 922
See Box 3-3 for explanation of atomic mass values used in this table
0.97 1.74
Sodium Magnesium 3 4 5 6 7 8 9
22.989 769 28 ±2 24.305 0 ±6
19 +1 20 +2 21 +3 22 +4,3 23 +5,4,3,2 24 +6,3,2 25 +7,6,4,2,3 26 +2,3 27 +2,3
1032 K 1757 Ca 3104 Sc 3562 Ti 3682 V 2945 Cr 2335 Mn 3135 Fe 3201 Co
336 1112 1812 1943 2175 2130 1517 1809 1768
0.86 1.55 3.0 4.50 5.8 7.19 7.43 7.86 8.90
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt
39.098 3 40.078 ±4 44.955 912 ±6 47.867 50.941 5 51.996 1 ±6 54.938 045 ±5 55.845 ±2 58.933 195 ±5
37 +1 38 +2 39 +3 40 +4 41 +5,3 42 +6,5,4,3,2 43 +7 44 +2,3,4,6,8 45 +2,3,4
961 Rb 1650 Sr 3611 Y 4682 Zr 5017 Nb 4912 Mo 4538 4423 Ru 3970 Rh
313 1041 1799 2125 2740 2890 2473 2523 2236
1.53 2.6 4.5 6.49 8.55 10.2 11.5 12.2 12.4
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium
85.467 8 ±3 87.62 88.905 85 ±2 91.224 ±2 92.906 38 ±2 95.96 ±2 (98) 101.07 ±2 102.905 50 ±2
55 +1 56 +2 57 +3 72 +4 73 +5 74 +6,5,4,3,2 75 +7,6,4,2,-1 76 +2,3,4,6,8 77 +2,3,4,6
944 Cs 2171 Ba 3730 La 4876 Hf 5731 Ta 5828 W 5869 Re 5285 Os 4701 Ir
302 1002 1193 2500 3287 3680 3453 3300 2716
1.87 3.5 6.7 13.1 16.6 19.3 21.0 22.4 22.5
Cesium Barium Lanthanum Hafnium Tantalum Tungsten Rhenium Osmium Iridium
132.905 451 9 ±2 137.327 ±7 138.905 47 ±7 178.49 ±2 180.947 88 ±2 183.84 186.207 190.23 ±3 192.217 ±3
87 +1 88 +2 89 [phone] 108 109
950 Fr 1809 Ra 3473 Ac —– —– —– —– —– —–
300 973 1323 —– —– —– —– —– —–
—– 5 10.07 —– —– —– —– —– —–
Francium Radium Actinium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium
(223) (226) (227) (267) (268) (271) (270) (277) (276)
58 +3,4 59 +3,4 60 +3 61 +3 62 +3,2 63 +3,2
3699 Ce 3785 Pr 3341 Nd 3785 2064Sm1870 Eu
1071 1204 1289 1204 1345 1090
6.78 6.77 7.00 6.48 7.54 5.26
Cerium Praseodymium Neodymium Promethium Samarium Europium
140.116 140.907 65 ±2 144.242 ±3 (145) 150.36 ±2 151.964
90 +4 91 +5,4 92 +6,5,4,3 93 +6,5,4,3 94 +6,5,4,3 95 +6,5,4,3
5061 Th —– Pa 4407 U —– 3503 2880
2028 —– 1405 910 913 1268
11.7 15.4 18.9 20.4 19.8 13.6
Thorium Protactinium Uranium Neptunium Plutonium Americium
232.038 06 ±2 231.035 88 ±2 238.028 91 ±3 (237) (244) (243)
18
of the Elements
2
4.2 He
0.95
¤
0.176
Atomic Mass Interval 13 14 15 16 17 Helium
H [1.007 84; 1.008 11] 4.002 602 ±2
Li [6.938; 6.997] 5 +3 6 ±4,2 7 ±3,5,4,2 8 -2 9 -1 10
B [10.806; 10.821]
C [12.009 6; 12.011 6] 42237050 B 44417000 C 7673 N 9500 O 8553 F 2275 Ne
N [14.006 43; 14.007 28] 2.34 2.62 1.234¤ 1.410¤ 1.674¤ 0.889¤
O [15.999 03; 15.999 77] Boron Carbon Nitrogen Oxygen Fluorine Neon
Si [28.084; 28.086] 10.814 ±8 12.010 6 ±10 14.006 8 ±4 15.999 4 ±4 18.998 403 2 ±5 20.179 7 ±6
S [32.059; 32.076]
13 +3 14 +4 15 ±3,5,4 16 ±2,4,6 17 ±1,3,5,7 18
Cl [35.446; 35.457]
Tl [204.382; 204.385] 2793 Al 3540 Si 550 P 718 S 239 Cl 87 Ar
933 1685 317 388 172 84
¤ ¤
2.70 2.33 1.82 2.07 3.12 1.760
10 11 12 Aluminum Silicon Phosphorus Sulfur Chlorine Argon
26.981 538 6 ±8 28.085 30.973 762 ±2 32.068 ±9 35.452 ±6 39.948
28 +2,3 29 +2,1 30 +2 31 +3 32 +4 33 ±3,5 34 -2,4,6 35 ±1,5 36
3187Ni 2836 Cu 1180 Zn 2478 Ga 3107 Ge 876 As 958 Se 332 Br 120 Kr
1726 1358 693 303 1210 —– 494 266 116
¤
8.90 8.96 7.14 5.91 5.32 5.72 4.80 3.12 3.69
Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
58.693 4 ±4 63.546 ±3 65.38 ±2 69.723 72.63 74.921 60 ±2 78.96 ±3 79.904 83.798 ±2
46 +2,4 47 +1 48 +2 49 +3 50 +4,2 51 ±3,5 52 -2,4,6 53 ±1,5,7 54
3237 Pd 2436 Ag 1040 Cd 2346 In 2876 Sn 1860 Sb 1261 Te 458 I 165 Xe
1825 1234 594 430 505 904 723 387 161
12.0 10.5 8.65 7.31 7.30 6.68 6.24 4.92 5.78¤
Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
106.42 107.868 2 ±2 112.411 ±8 114.818 ±3 118.710 ±7 121.760 127.60 ±3 126.904 47 ±3 131.293 ±6
78 +2,4 79 +3,1 80 +2,1 81 +3,1 82 +4,2 83 +3,5 84 +4,2 85 ±1,3,5,7 86
4100 Pt 3130 Au 630 Hg 1746 Tl 2023 Pb 1837 Bi 1235 Po 610 At 211 Rn
2045 1338 234 577 601 545 527 575 202
¤
21.4 19.3 13.5 11.85 11.4 9.8 9.4 —– 9.78
Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon
195.084 ±9 196.966 569 ±4 200.59 ±2 204.384 ±2 207.2 208.980 40 (209) (210) (222)
110 111 112 113 114 115 116 117 118
—– —– —– —– —–
—– —– —– —– —–
—– —– —– —– —–
Darmstadtium Roentgenium Copernicium Flerovium Livermorium
(281) (280) (285) (284) (289) (288) (293) (294) (294)
64 +3 65 +3,4 66 +3 67 +3 68 +3 69 +3,2 70 +3,2 71 +3
3539 Gd 3496 Tb 2835 Dy 2968 Ho 3136 Er 2220 Tm 1467 Yb 3668 Lu
1585 1630 1682 1743 1795 1818 1097 1936
7.89 8.27 8.54 8.80 9.05 9.33 6.98 9.84
Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium
157.25 ±3 158.925 35 ±2 162.500 164.930 32 ±2 167.259 ±3 168.934 21 ±2 173.054 ±5 174.966 8
96 +3 97 +4,3 98 [phone]
—– —– —– —– —– —– —– —–
1340 —– 900 —– —– —– —– —–
13.5 —– —– —– —– —– —– —–
Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium
(247) (247) (251) (252) (257) (260) (259) (262)
Quantitative Chemical Analysis
[© 1963 by Sempé and Éditions Denoël.]
Quantitative
Chemical Analysis
Ninth Edition
Daniel C. Harris
Michelson Laboratory, China Lake, California
Charles A. Lucy
Contributing Author
University of Alberta, Edmonton, Alberta
Publisher: Kate Parker
Senior Acquisitions Editor: Lauren Schultz
Development Editors: Brittany Murphy, Anna Bristow
Editorial Assistant: Shannon Moloney
Photo Editor: Cecilia Varas
Photo Researcher: Richard Fox
Cover and Text Designer: Vicki Tomaselli
Project Editor: J. Carey Publishing Service
Manuscript Editor: Marjorie Anderson
Illustrations: Network Graphics, Precision Graphics
Illustration Coordinators: Matthew McAdams, Janice Donnola
Production Coordinator: Julia DeRosa
Composition and Text Layout: Aptara®, Inc.
Printing and Binding: RR Donnelley
Front Cover/Title Page Photo Credit: © The Natural History Museum/The Image Works
Back Cover Photo Credit: Pascal Goetgheluck/Science Source
Library of Congress Control Number: 2014950382
ISBN-13: 978-1-4641-3538-5
ISBN-10: 1-4641-3538-X
© 2016, 2010, 2007, 2003 by W. H. Freeman and Company
All rights reserved
Printed in the United States of America
First Printing
W. H. Freeman and Company
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www.whfreeman.com
BRIEF CONTENTS
0 The Analytical Process 1 17 Electroanalytical Techniques 395
1 Chemical Measurements 10 18 Fundamentals of
Spectrophotometry 432
2 Tools of the Trade 24
19 Applications of
3 Experimental Error 46 Spectrophotometry 461
4 Statistics 64 20 Spectrophotometers 491
5 Quality Assurance and
21 Atomic Spectroscopy 529
Calibration Methods 95
22 Mass Spectrometry 559
6 Chemical Equilibrium 119
23 Introduction to Analytical
7 Let the Titrations Begin 145 Separations 604
8 Activity and the Systematic
24 Gas Chromatography 633
Treatment of Equilibrium 161
25 High-Performance Liquid
9 Monoprotic Acid-Base
Chromatography 667
Equilibria 187
26 Chromatographic Methods
10 Polyprotic Acid-Base
and Capillary Electrophoresis 713
Equilibria 211
27 Gravimetric and Combustion
11 Acid-Base Titrations 233 Analysis 751
12 EDTA Titrations 265 28 Sample Preparation 771
13 Advanced Topics in
Equilibrium 287 Notes and References NR1
Glossary GL1
14 Fundamentals of
Electrochemistry 306 Appendixes AP1
15 Electrodes and Solutions to Exercises S1
Potentiometry 338
Answers to Problems AN1
16 Redox Titrations 374 Index I1
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CONTENTS
Connections: Maria Goeppert Mayer xiv 4 Statistics 64
Preface xv
Is My Red Blood Cell Count High Today? 64
0 The Analytical Process 1 4-1 Gaussian Distribution 65
4-2 Comparison of Standard Deviations
How Does a Home Pregnancy Test Work? 1 with the F Test 69
0-1 The Analytical Chemist’s Job 2 BOX 4-1 C hoosing the Null Hypothesis in
0-2 General Steps in a Chemical Analysis 8 Epidemiology 71
BOX 0-1 Constructing a Representative Sample 8 4-3 Confi dence Intervals 71
4-4 Comparison of Means with Student’s t 74
1 Chemical Measurements 10
4-5 t Tests with a Spreadsheet 79
4-6 Grubbs Test for an Outlier 80
Biochemical Measurements with a Nanoelectrode 10
4-7 The Method of Least Squares 81
1-1 SI Units 10
4-8 Calibration Curves 84
1-2 Chemical Concentrations 13
1-3 Preparing Solutions 16 BOX 4-2 U sing a Nonlinear Calibration Curve 86
4-9 A Spreadsheet for Least Squares 87
1-4 Stoichiometry Calculations for
Gravimetric Analysis 18
5 Quality Assurance and
2 Tools of the Trade 24 Calibration Methods 95
Quartz Crystal Microbalance Measures The Need for Quality Assurance 95
One Base Added to DNA 24
5-1 Basics of Quality Assurance 96
2-1 Safe, Ethical Handling of Chemicals
BOX 5-1 M edical Implication of False
and Waste 25
Positive Results 97
2-2 The Lab Notebook 25
BOX 5-2 Control Charts 99
2-3 Analytical Balance 26
5-2 Method Validation 100
2-4 Burets 29
BOX 5-3 T he Horwitz Trumpet: Variation in
2-5 Volumetric Flasks 31
Interlaboratory Precision 104
2-6 Pipets and Syringes 32
5-3 Standard Addition 106
2-7 Filtration 36
5-4 Internal Standards 109
2-8 Drying 37
2-9 Calibration of Volumetric Glassware 38
6 Chemical Equilibrium 119
2-10 Introduction to Microsoft Excel® 39
2-11 Graphing with Microsoft Excel 42 Chemical Equilibrium in the Environment 119
REFERENCE PROCEDURE Calibrating a 50-mL Buret 45 6-1 The Equilibrium Constant 120
6-2 Equilibrium and Thermodynamics 121
3 Experimental Error 46
6-3 Solubility Product 124
Experimental Error 46 BOX 6-1 S olubility Is Governed by More Than the
Solubility Product 125
3-1 Signifi cant Figures 46
3-2 Signifi cant Figures in Arithmetic 47 DEMONSTRATION 6-1 Common Ion Effect 125
6-4 Complex Formation 126
3-3 Types of Error 49
BOX 3-1 C ase Study in Ethics: Systematic Error BOX 6-2 Notation for Formation Constants 127
in Ozone Measurement 50 6-5 Protic Acids and Bases 129
BOX 3-2 Certifi ed Reference Materials 51 6-6 pH 132
6-7 Strengths of Acids and Bases 133
3-4 Propagation of Uncertainty from
Random Error 52 DEMONSTRATION 6-2 The HCl Fountain 134
3-5 Propagation of Uncertainty from BOX 6-3 T he Strange Behavior of
Systematic Error 58 Hydrofl uoric Acid 135
BOX 3-3 Atomic Masses of the Elements 59 BOX 6-4 Carbonic Acid 137
vii