Quantitative Chemical Analysis 9th

Edition by Daniel C. Harris (eBook PDF)

Visit to download the full and correct content document:
https://ebooksecure.com/download/quantitative-chemical-analysis-9th-edition-by-dani
el-c-harris-ebook-pdf/
 B R I E F C O N TE N TS

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

v
this  page  left  intentionally  blank
 CO NTE N TS

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 Choosing 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 Confidence 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 Using a Nonlinear Calibration Curve 86
1-4 Stoichiometry Calculations for 4-9 A Spreadsheet for Least Squares 87
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 Medical 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 The 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
2-10 Introduction to Microsoft Excel® 39
6 Chemical Equilibrium 119
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 Solubility Is Governed by More Than the

3-1 Significant Figures 46 Solubility Product 125

3-2 Significant Figures in Arithmetic 47 DEMONSTR ATION 6-1 Common Ion Effect 125
3-3 Types of Error 49 6-4 Complex Formation 126
BOX 3-1 Case 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 Certified Reference Materials 51 6-6 pH 132
3-4 Propagation of Uncertainty from 6-7 Strengths of Acids and Bases 133
Random Error 52 DEMONSTR ATION 6-2 The HCl Fountain 134
3-5 Propagation of Uncertainty from BOX 6-3 The Strange Behavior of
Systematic Error 58 Hydrofluoric Acid 135
BOX 3-3 Atomic Masses of the Elements 59 BOX 6-4 Carbonic Acid 137

vii
7 Let the Titrations Begin 145 10-5 Fractional Composition Equations 223
BOX 10 -3 Microequilibrium Constants 224
Titration on Mars 145 10-6 Isoelectric and Isoionic pH 226
7-1 Titrations 145 BOX 10 -4 Isoelectric Focusing 228
BOX 7-1 Reagent Chemicals and Primary Standards 147
7-2 Titration Calculations 147 11 Acid-Base Titrations 233
7-3 Precipitation Titration Curves 149
7-4 Titration of a Mixture 153 Acid-Base Titration of RNA 233
7-5 Calculating Titration Curves with a Spreadsheet 154 11-1 Titration of Strong Base with Strong Acid 234
7-6 End-Point Detection 155 11-2 Titration of Weak Acid with Strong Base 236
DEMONSTR ATION 7-1 Fajans Titration 156 11-3 Titration of Weak Base with Strong Acid 238
11-4 Titrations in Diprotic Systems 240
11-5 Finding the End Point with a
8 Activity and the Systematic pH Electrode 243
Treatment of Equilibrium 161 BOX 11-1 Alkalinity and Acidity 244
Hydrated Ions 161 11-6 Finding the End Point with Indicators 247
8-1 The Effect of Ionic Strength on BOX 11-2 What Does a Negative pH Mean? 248
Solubility of Salts 162 DEMONSTR ATION 11-1 Indicators and the
DEMONSTR ATION 8-1 Effect of Ionic Strength on Ion Acidity of CO2 249
Dissociation 162 11-7 Practical Notes 251
BOX 8-1 Salts with Ions of Charge ) $ 2 ) Do Not 11-8 Kjeldahl Nitrogen Analysis 251
Fully Dissociate 164 BOX 11-3 Kjeldahl Nitrogen Analysis Behind
8-2 Activity Coefficients 164 the Headlines 252
8-3 pH Revisited 168 11-9 The Leveling Effect 253
8-4 Systematic Treatment of Equilibrium 169 11-10 Calculating Titration Curves with
BOX 8-2 Calcium Carbonate Mass Balance in Rivers 172 Spreadsheets 254
8-5 Applying the Systematic Treatment REFERENCE PROCEDURE Preparing Standard Acid
of Equilibrium 172 and Base 263

9 Monoprotic Acid-Base Equilibria 187 12 EDTA Titrations 265

Measuring pH Inside Cellular Compartments 187 Chelation Therapy and Thalassemia 265
9-1 Strong Acids and Bases 188 12-1 Metal-Chelate Complexes 266
12-2 EDTA 268
BOX 9-1 Concentrated HNO3 Is Only
Slightly Dissociated 188 12-3 EDTA Titration Curves 271
9-2 Weak Acids and Bases 190 12-4 Do It with a Spreadsheet 273
9-3 Weak-Acid Equilibria 191 12-5 Auxiliary Complexing Agents 274
BOX 12-1 Metal Ion Hydrolysis Decreases
BOX 9-2 Dyeing Fabrics and the Fraction
the Effective Formation Constant
of Dissociation 194
for EDTA Complexes 276
9-4 Weak-Base Equilibria 195
12-6 Metal Ion Indicators 277
9-5 Buffers 196
DEMONSTR ATION 12-1 Metal Ion Indicator Color
BOX 9-3 Strong Plus Weak Reacts Completely 199
Changes 280
DEMONSTR ATION 9-1 How Buffers Work 201
12-7 EDTA Titration Techniques 280
BOX 12-2 Water Hardness 281
10 Polyprotic Acid-Base Equilibria 211
Carbon Dioxide in the Air 211 13 Advanced Topics in Equilibrium 287
10-1 Diprotic Acids and Bases 212 Acid Rain 287
BOX 10 -1 Carbon Dioxide in the Ocean 214 13-1 General Approach to Acid-Base Systems 288
BOX 10 -2 Successive Approximations 217 13-2 Activity Coefficients 291
10-2 Diprotic Buffers 219 13-3 Dependence of Solubility on pH 294
10-3 Polyprotic Acids and Bases 220 13-4 Analyzing Acid-Base Titrations with
10-4 Which Is the Principal Species? 222 Difference Plots 298

viii Contents
14 Fundamentals of 16-3 Adjustment of Analyte Oxidation State 381
16-4 Oxidation with Potassium Permanganate 382
Electrochemistry 306 16-5 Oxidation with Ce41 384
Lithium-Ion Battery 306 16-6 Oxidation with Potassium Dichromate 385
14-1 Basic Concepts 307 16-7 Methods Involving Iodine 385
BOX 14-1 Ohm’s Law, Conductance, and BOX 16-2 Environmental Carbon Analysis and
Molecular Wire 310 Oxygen Demand 386
14-2 Galvanic Cells 311 BOX 16-3 Iodometric Analysis of High-Temperature
DEMONSTR ATION 14-1 The Human Salt Bridge 314 Superconductors 389
BOX 14-2 Hydrogen-Oxygen Fuel Cell 315
BOX 14-3 Lead-Acid Battery 316 17 Electroanalytical Techniques 395
14-3 Standard Potentials 316
How Sweet It Is! 395
14-4 Nernst Equation 318
17-1 Fundamentals of Electrolysis 396
BOX 14-4 E° and the Cell Voltage Do Not Depend
DEMONSTR ATION 17-1 Electrochemical Writing 396
on How You Write the Cell Reaction 320
BOX 17-1 Metal Reactions at Atomic Steps 402
BOX 14-5 Latimer Diagrams: How to Find E°
17-2 Electrogravimetric Analysis 402
for a New Half-Reaction 321
17-3 Coulometry 405
14-5 E° and the Equilibrium Constant 322
17-4 Amperometry 407
BOX 14-6 Concentrations in the Operating Cell 323
BOX 17-2 Clark Oxygen Electrode 408
14-6 Cells as Chemical Probes 324
14-7 Biochemists Use E°' 327
BOX 17-3 What Is an “Electronic Nose”? 408
17-5 Voltammetry 412
BOX 17-4 The Electric Double Layer 415
15 Electrodes and Potentiometry 338
BOX 17-5 Aptamer Biosensor for Clinical Use 417
DNA Sequencing by Counting Protons 338 17-6 Karl Fischer Titration of H2O 422
15-1 Reference Electrodes 339
15-2 Indicator Electrodes 341 18 Fundamentals of
DEMONSTR ATION 15-1 Potentiometry with an Spectrophotometry 432
Oscillating Reaction 343
15-3 What Is a Junction Potential? 343 The Ozone Hole 432
15-4 How Ion-Selective Electrodes Work 345 18-1 Properties of Light 433
15-5 pH Measurement with a Glass Electrode 347 18-2 Absorption of Light 434
BOX 15-1 Systematic Error in Rainwater pH BOX 18-1 Why Is There a Logarithmic Relation
Measurement: Effect of Junction Potential 353 Between Transmittance and Concentration? 436
15-6 Ion-Selective Electrodes 354 DEMONSTR ATION 18-1 Absorption Spectra 438
BOX 15-2 Measuring Selectivity Coefficients for 18-3 Measuring Absorbance 438
an Ion-Selective Electrode 355 18-4 Beer’s Law in Chemical Analysis 440
BOX 15-3 How Was Perchlorate Discovered on Mars? 359 18-5 Spectrophotometric Titrations 443
BOX 15-4 Ion-Selective Electrode with Electrically 18-6 What Happens When a Molecule
Conductive Polymer for a Sandwich Absorbs Light? 444
Immunoassay 361 BOX 18-2 Fluorescence All Around Us 447
15-7 Using Ion-Selective Electrodes 363 18-7 Luminescence 448
15-8 Solid-State Chemical Sensors 364 BOX 18-3 Rayleigh and Raman Scattering 452
BOX 18-4 Designing a Molecule for Fluorescence
16 Redox Titrations 374 Detection 454

Chemical Analysis of High-Temperature 19 Applications of Spectrophotometry 461

Superconductors 374
16-1 The Shape of a Redox Titration Curve 375 Fluorescence Resonance Energy Transfer Biosensor 461
BOX 16-1 Many Redox Reactions Are Atom-Transfer 19-1 Analysis of a Mixture 461
Reactions 376 19-2 Measuring an Equilibrium Constant 466
16-2 Finding the End Point 378 19-3 The Method of Continuous Variation 470
DEMONSTR ATION 16-1 Potentiometric Titration 19-4 Flow Injection Analysis and Sequential
of Fe21 with MnO24 379 Injection 471

Contents ix
 19-5 Immunoassays 475 BOX 22-5 Making Elephants Fly (Mechanisms of
19-6 Sensors Based on Luminescence Quenching 477 Protein Electrospray) 588
BOX 19-1 Converting Light into Electricity 478 22-6 Open-Air Sampling for Mass Spectrometry 592
BOX 19-2 Upconversion 482 22-7 Ion Mobility Spectrometry 594

20 Spectrophotometers 491 23 Introduction to Analytical

Cavity Ring-Down Spectroscopy 491 Separations 604
20-1 Lamps and Lasers: Sources of Light 492 Milk Does a Baby Good 604
BOX 20 -1 Blackbody Radiation and the 23-1 Solvent Extraction 604
Greenhouse Effect 494
DEMONSTR ATION 23-1 Extraction with Dithizone 607
20-2 Monochromators 496
BOX 23-1 Crown Ethers and Phase Transfer Agents 609
20-3 Detectors 501
23-2 What Is Chromatography? 609
BOX 20 -2 The Most Important Photoreceptor 502
23-3 A Plumber’s View of Chromatography 611
BOX 20 -3 Nondispersive Photoacoustic Infrared
23-4 Efficiency of Separation 615
Measurement of CO2 on Mauna Loa 507
23-5 Why Bands Spread 621
20-4 Optical Sensors 508
BOX 23-2 Microscopic Description of
20-5 Fourier Transform Infrared Spectroscopy 514
Chromatography 626
20-6 Dealing with Noise 519

21 Atomic Spectroscopy 529 24 Gas Chromatography 633

An Anthropology Puzzle 529 Doping in Sports 633
21-1 An Overview 530 24-1 The Separation Process in Gas
Chromatography 634
BOX 21-1 Mercury Analysis by Cold Vapor
Atomic Fluorescence 532 BOX 24-1 Chiral Phases for Separation Optical

21-2 Atomization: Flames, Furnaces, and Plasmas 532 Isomers 638

24-2 Sample Injection 645
BOX 21-2 Measuring Sodium with a Bunsen
Burner Photometer 534 24-3 Detectors 648
21-3 How Temperature Affects Atomic Spectroscopy 539 BOX 24-2 Chromatography Column on a Chip 652
21-4 Instrumentation 540 24-4 Sample Preparation 655
21-5 Interference 544 24-5 Method Development in Gas
21-6 Sampling by Laser Ablation 546 Chromatography 657
21-7 Inductively Coupled Plasma–Mass BOX 24-3 Two-Dimensional Gas
Spectrometry 547 Chromatography 660
BOX 21-3 Atomic Emission Spectroscopy on Mars 548
21-8 X-ray Fluorescence 550 25 High-Performance Liquid
Chromatography 667
22 Mass Spectrometry 559
Paleothermometry: How to Measure Historical
Droplet Electrospray 559 Ocean Temperatures 667
22-1 What Is Mass Spectrometry? 559 25-1 The Chromatographic Process 668
BOX 22-1 Molecular Mass and Nominal Mass 561 BOX 25-1 One-Million-Plate Colloidal Crystal
BOX 22-2 How Ions of Different Masses Are Separated Columns Operating by Slip Flow 676
by a Magnetic Field 561 BOX 25-2 Structure of the Solvent–Bonded
22-2 Oh, Mass Spectrum, Speak to Me! 564 Phase Interface 677
BOX 22-3 Isotope Ratio Mass Spectrometry and BOX 25-3 “Green” Technology: Supercritical Fluid
Dinosaur Body Temperature 566 Chromatography 680
22-3 Types of Mass Spectrometers 571 25-2 Injection and Detection in HPLC 685
22-4 Chromatography–Mass Spectrometry 25-3 Method Development for Reversed-Phase
Interfaces 579 Separations 691
22-5 Chromatography–Mass Spectrometry 25-4 Gradient Separations 699
Techniques 583 25-5 Do it with a Computer 701
BOX 22-4 Matrix-Assisted Laser Desorption/ BOX 25-4 Choosing Gradient Conditions and
Ionization 588 Scaling Gradients 704

x Contents
26 Chromatographic Methods and 28 Sample Preparation 771
Capillary Electrophoresis 713 Cocaine Use? Ask the River 771
DNA Profiling 713 28-1 Statistics of Sampling 773
26-1 Ion-Exchange Chromatography 714 28-2 Dissolving Samples for Analysis 777
26-2 Ion Chromatography 720 28-3 Sample Preparation Techniques 782
BOX 26-1 Surfactants and Micelles 725
Notes and References NR1
26-3 Molecular Exclusion Chromatography 725
Glossary GL1
26-4 Affinity Chromatography 727
Appendixes AP1
BOX 26-2 Molecular Imprinting 728 A. Logarithms and Exponents and Graphs
26-5 Hydrophobic Interaction Chromatography 728 of Straight Lines AP1
26-6 Principles of Capillary Electrophoresis 729 B. Propagation of Uncertainty AP3
26-7 Conducting Capillary Electrophoresis 735 C. Analysis of Variance and Efficiency in
26-8 Lab-on-a-Chip: DNA Profiling 743 Experimental Design AP10
D. Oxidation Numbers and Balancing Redox Equations AP19
27 Gravimetric and E. Normality AP22
Combustion Analysis 751 F. Solubility Products AP23
G. Acid Dissociation Constants AP25
The Geologic Time Scale and Gravimetric Analysis 751
H. Standard Reduction Potentials AP34
27-1 An Example of Gravimetric Analysis 752
I. Formation Constants AP42
27-2 Precipitation 754
J. Logarithm of the Formation Constant for
DEMONSTR ATION 27-1 Colloids, Dialysis, and
the Reaction M(aq) 1 L(aq) Δ ML(aq) AP45
Microdialysis 755
K. Analytical Standards AP46
BOX 27-1 van der Waals Attraction 758 L. DNA and RNA AP48
27-3 Examples of Gravimetric Calculations 760 Solutions to Exercises S1
27-4 Combustion Analysis 763 Answers to Problems AN1
Index I1

Contents xi
 EXP E R I M E N TS

Experiments are found at the website 21. Microscale Spectrophotometric Measurement of Iron in
www.whfreeman.com/qca/ Foods by Standard Addition
22. Spectrophotometric Measurement of an Equilibrium
0. Green Analytical Chemistry Constant
1. Calibration of Volumetric Glassware 23. Spectrophotometric Analysis of a Mixture: Caffeine and
2. Gravimetric Determination of Calcium as CaC2O4 ? H2O Benzoic Acid in a Soft Drink
3. Gravimetric Determination of Iron as Fe2O3 24. Mn21 Standardization by EDTA Titration
4. Penny Statistics 25. Measuring Manganese in Steel by Spectrophotometry with
5. Statistical Evaluation of Acid-Base Indicators Standard Addition
6. Preparing Standard Acid and Base 26. Measuring Manganese in Steel by Atomic Absorption
7. Using a pH Electrode for an Acid-Base Titration Using a Calibration Curve
8. Analysis of a Mixture of Carbonate and Bicarbonate 27. Properties of an Ion-Exchange Resin
9. Analysis of an Acid-Base Titration Curve: The Gran Plot 28. Analysis of Sulfur in Coal by Ion Chromatography
10. Fitting a Titration Curve with Excel Solver 29. Measuring Carbon Monoxide in Automobile Exhaust
11. Kjeldahl Nitrogen Analysis by Gas Chromatography
12. EDTA Titration of Ca21 and Mg21 in Natural Waters 30. Amino Acid Analysis by Capillary Electrophoresis
13. Synthesis and Analysis of Ammonium Decavanadate 31. DNA Composition by High-Performance Liquid
14. Iodimetric Titration of Vitamin C Chromatography
15. Preparation and Iodometric Analysis of High-Temperature 32. Analysis of Analgesic Tablets by High Performance Liquid
Superconductor Chromatography
16. Potentiometric Halide Titration with Ag1 33. Anion Content of Drinking Water by Capillary
17. Electrogravimetric Analysis of Copper Electrophoresis
18. Polarographic Measurement of an Equilibrium Constant 34. Green Chemistry: Liquid Carbon Dioxide Extraction
19. Coulometric Titration of Cyclohexene with Bromine of Lemon Peel Oil
20. Spectrophotometric Determination of Iron in Vitamin
Tablets

SP R E A D S H E E T TO P I C S

2-10 Introduction to Microsoft Excel 39 8-5 Goal Seek 174

2-11 Graphing with Microsoft Excel 42 8-5 Solver 176–177
Problem 3-8 Controlling the appearance of a graph 61 8-5 Solver with circular reference 179
4-1 Average, standard deviation 66 9-5 Excel’s Goal Seek tool and naming of cells 206
4-1 Area under a Gaussian curve (Normdist) 67 Problem 10-9 Automatic iteration 230
Table 4-3 F-Distribution (Finv) 70 11-10 Acid-base titration 254
4-3 Finding Confidence Intervals 73 12-4 EDTA titrations 273
4-4 Paired t-Test 77 Problem 12-20 Auxiliary complexing agents in
4-5 t-Test 79 EDTA titrations 284
4-7 Equation of a straight line (Slope and Intercept) 82 Problem 12-22 Complex formation 285
4-7 Equation of a straight line (LINEST) 84 13-1 Using Excel Solver 290
4-9 Spreadsheet for least squares 87 13-2 Activity coefficients with the
4-9 Error bars on graphs 88 Davies equation 291–293
5-2 Square of the correlation coefficient, R2 13-3 Dependence of solubility on pH 296
(LINEST) 101 13-4 Fitting nonlinear curves by least squares 301
Problem 5-15 Using Trendline 114 13-4 Using Excel Solver for more than one unknown 302
7-5 Calculating precipitation titration curves 19-1 Solving simultaneous equations by least
with a spreadsheet 154 squares with Solver 463

xii Spreadsheet Topics

19-1 Solving simultaneous equations by matrix
inversion
19-2 Measuring equilibrium constants by least
squares with Solver
20-6 Savitzky-Golay polynomial smoothing of noise
25-5 Computer simulation of a chromatogram
Appendix B Propagation of uncertainty
Appendix C Analysis of variance (ANOVA) AP13–AP14
S P R E A D S H E E TS AT WEB SIT E
Figure 4-10 t-Test
Figure 4-15 Least Squares with LINEST
Figure 4-16 Error Bar Graph
Figure 5-5 Standard Addition with Graph
Figure 6-3 Complex Formation
Figure 8-13 CaSO4 Equilibria
Problem 8-30 MgCl2 Ion Pairing with Activity
Figure 11-3a Titration of HA with NaOH Effect of pKa
Figure 11-3a Titration of HA with NaOH Effect of
Concentration
Figure 11-4 Nicotine Titration
Figure 12-12 EDTA Titration
Figure 13-1 Tartrate 1 Pyridinium 1 OH2
Figure 13-3 KH2PO4 1 Na2HPO4 with Activity
Spreadsheets at Website
Appendix C Multiple linear regression and experimental
465 design (Linest) AP15
Supplementary Topics at Website:
467 Spreadsheet for Precipitation Titration of a Mixture
521 Microequilibrium Constants
701 Spreadsheets for Redox Titration Curves
AP4 HPLC Chromatography Simulator
Fourier Transform of Infrared Spectrum with a Spreadsheet
Figure 13-5 CaF2 with Activity
Figure 13-6 Barium Oxalate
Figure 13-11 Difference Plot for Glycine
Figure 19-3 Analysis of Mixture
(More Points than Components)
Figure 19-4 Solving Two Simultaneous Equations
Figure 19-8 Neutral Red Protein Binding Least Squares
Exercise 19-B Data for Analysis of Three-
Component Mixture
Figure 25-36 Isocratic Chromatogram Simulator
Supplement: Gradient Elution Chromatogram Simulator
Supplement: FTIR Interferogram
Supplement: FTIR Interferogram Solution for Exercise
xiii
 CONNECTIONS: Maria Goeppert Mayer

Maria Goeppert Mayer (1906–1972) was the second and,

so far, last woman (after Marie Curie) to receive the Nobel
Prize in Physics. She shared half of the 1963 prize with
Hans Jensen for their independent theories of atomic
nuclear shell structure published in 1949.
What does she have to do with this book? The back
cover shows evidence that the body temperature of certain
dinosaurs was similar to that of warm blooded animals. In
1947, she and Jacob Bigeleisen published a paper,
“Calculation of Equilibrium Constants for Isotopic
[Emilio Segre Visual Archives/ Exchange Reactions.”* This paper was one of the founda-
Science Source.]
tional studies for paleothermometry—the use of isotopes
to deduce the temperature at which objects such as dinosaur teeth were formed. From
mathematical physics to analytical chemistry to dinosaurs, there is a thread of connection.
Maria was born to a sixth-generation university professor in Göttingen, Germany.†
From early childhood, she knew that she would acquire a university education, but there
were few avenues for girls’ education. She attended a small, private girls’ school, which
closed before her studies were complete. Against all advice, she took and passed the
University of Göttingen entrance examination to be admitted in 1924. Her first exposure to
quantum mechanics by Max Born hooked her. She received a Ph.D. in 1930, with three
Nobel Prize winners on her committee.
Maria married Joe Mayer, a Caltech- and Berkeley-educated physical chemist who was a
postdoctoral boarder in the Goeppert household. They moved to the U.S., where Joe began a
distinguished career at Johns Hopkins University, Columbia University, and the University of
Chicago. In 1940 they coauthored Statistical Mechanics, a textbook used for more than
40 years. Maria was regarded as at least equally gifted, but she was not offered a paid posi-
tion at any university despite teaching courses, advising graduate students, serving on com-
mittees, and writing graduate examinations—all as a volunteer! Her first paid appointment as
a professor at the University of California at San Diego came in 1960, four years after her
election to the National Academy of Sciences.

*J. Bigeleisen and M. G. Mayer, J. Chem. Phys. 1947, 15, 261.

†
S. B. McGrayne, Nobel Prize Women in Science (Washington DC: Joseph Henry Press, 1998).

xiv
 P R E FAC E

Goals of This Book

My goals are to provide a sound physical understanding of the principles of analytical chem-
istry and to show how these principles are applied in chemistry and related disciplines—
especially in life sciences and environmental science. I have attempted to present the subject
in a rigorous, readable, and interesting manner, lucid enough for nonchemistry majors, but
containing the depth required by advanced undergraduates. This book grew out of an intro-
ductory analytical chemistry course that I taught mainly for nonmajors at the University of
California at Davis and from a course for third-year chemistry students at Franklin and
Marshall College in Lancaster, Pennsylvania.

What’s New?
Beginning with dinosaur body temperature on the back cover of this book, analytical chemis-
try addresses interesting questions in the wider world. The facing page draws a connection
between the back cover and underlying human achievement in physics that enables us to
deduce body temperature from the isotopic composition of teeth. The story of Maria Goeppert
Mayer is a lesson for us all in how women in science were so poorly treated not so long ago.
In this edition, the introduction to titrations has been consolidated in Chapter 7. Acid-
base, EDTA, redox, and spectrophotometric titrations are still treated in other chapters. The
power of the spreadsheet is unleashed in Chapter 8 to reach numerical solutions to equilib-
rium problems and in Chapter 19 to compute equilibrium constants from spectrophotometric
data. Atomic spectroscopy Chapter 21 has a new section on X-ray fluorescence as a routine
analytical tool. Mass spectrometry Chapter 22 has been expanded to increase the level of
detail and to help keep up with new developments. Chapter 27 has an extraordinary sequence
of micrographs showing the onset of crystallization of a precipitate. Three new methods in
sample preparation were added to Chapter 28. Appendix B takes a deeper look at propagation
of uncertainty and Appendix C treats analysis of variance.

Container with
leaching solution
− 1.0
Leaching solution added
Cl − calibration Cl −
solution added
− 2.0
log (concentration, M)

Actuator arm
to deliver Soil added and
canisters of BaCl2 begins to Cl − = 0.009 6 M
Stainless dry reagents enter cell at end point
steel sieve − 3.0
to reject
large chunks
of soil Cl − = 0.000 19 M
before BaCl2 addition Ba2+
− 4.0

Beaker End point

compartment − 5.0
0:00 2:00 4:00 6:00 8:00 10:00 12:00 14:00 16:00
Time (h)

BOX 15-3 Measuring sulfate on Mars by FIGURE FROM PROBLEM 7-21 Barium sulfate
titration with barium [Mars Lander: NASA/JPL-Caltech/ precipitation titration from Phoenix Mars Lander [Data
University of Arizona/Max Planck Institute.] courtesy S. Kounaves, Tufts University.]

For the first time since I began work on this book in 1978, I have taken on a contributing
author for part of this revision. Professor Chuck Lucy of the University of Alberta shares his
expertise and teaching experience with us in Chapters 23–26 on chromatography and capil-
lary electrophoresis. He improved the discussion of the efficiency of separation and mecha-
nisms of band spreading. Emphasis is placed on types of interactions between solutes and the
stationary phase. Types of solvent polarity are distinguished in liquid chromatography.
Examples are given for the selection of stationary phase and pH for liquid chromatography
separations. Electrophoresis has more emphasis on the effects of ion size and pH on mobility.
Chuck contributes the views of a specialist in separation science to these chapters.
New boxed applications include a home pregnancy test (Chapter 0 opener), observing the
addition of one base to DNA with a quartz crystal microbalance (Chapter 2 opener), medical
implications of false positive results (Box 5-1), a titration on Mars (Chapter 7 opener),

xv
 Cl −
AuCl4−

FIGURE FROM BOX 17-1 Anodic dissolution of gold at atomic steps [R. Wen, A.
Lahiri, M. Azhagurajan, S. Kobayashi, K. Itaya, “A New in situ Optical Microscope with Single Atomic
Layer Resolution for Observation of Electrochemical Dissolution of Au (111),” J Am Chem Soc 2010,
132,13657, Figure 2. Reprinted with permission © 2010, American Chemical Society.]

microequilibrium constants (Box 10-3), acid-base titration of RNA to provide evidence for
the mechanism of RNA catalysis (Chapter 11 opener), the hydrogen-oxygen fuel cell and the
Apollo 13 accident (Box 14-2), the lead-acid battery (Box 14-3), high-throughput DNA
sequencing by counting protons (Chapter 15 opener), how perchlorate was discovered on
Mars (Box 15-3), ion-selective electrode with a conductive polymer for a sandwich immuno-
assay (Box 15-4), metal reaction at atomic steps (Box 17-1), an aptamer biosensor for
clinical use (Box 17-5), Bunsen burner flame photometer (Box 21-2), atomic emission
spectroscopy on Mars (Box 21-3), making elephants fly (mechanism of protein electrospray,
Box 22-5), chromatographic analysis of breast milk (Chapter 23 opener), doping in sports
(Chapter 24 opener), two-dimensional gas chromatography (Box 24-3), million-plate separa-
tion by slip flow chromatography (Box 25-1), forensic DNA profiling (Chapter 26 opener
and Section 26-8), and measuring van der Waals attraction (Box 27-1). New Color Plates
illustrate the effect of ionic strength on ion dissociation (Color Plate 4), the mechanism of
chromatography by partitioning of analyte between phases (Color Plate 30), and separation
of dyes by solid-phase extraction (Color Plate 36).

5 Metabolite
A Reference
compound 1
Metabolite
Column 2 retention time (s)

4 E

Reference
1 compound 2
Interferent

0
10 15 20 25
Column 1 retention time (min)

CHAPTER 24 OPENING IMAGE Two-dimensional gas chromatography—

combustion isotope ratio mass spectrometry to detect doping in athletes
[H. J. Tobias, Y. Zhang, R. J. Auchus, J. T. Brenna, “Detection of Synthetic Testosterone
Use by Novel Comprehensive Two-Dimensional Gas Chromatography Combustion
Isotope Ratio Mass Spectrometry,” Anal Chem 2011, 83, 7158, Figure 4A. Reprinted
with permission © 2011, American Chemical Society.]

Pedagogical changes in this edition include more discussion of serial dilution to prepare
standards in Chapters 2, 3, and 18, distinction between standard uncertainty and standard
deviation in statistics, more discussion of hypothesis testing in statistics, employing the F
test before the t test for comparison of means, using a graphical treatment for internal stan-
dards, emphasis on electron flow toward the more positive electrode in electrochemical
cells, using nanoscale observations to probe phenomena such as van der Waals forces and

xvi Preface
the amorphous structure of glass in a pH electrode, polynomial
smoothing of noisy data, expanded discussion of the time-of-
flight mass spectrometer and ion mobility separations, enhanced
discussion of intermolecular forces in chromatography, enhanced
discussion of method development in liquid chromatography,
use of a free, online liquid chromatography simulator, introduc-
tion of two literature search questions in chromatography, and
taking more advantage of the power of Excel for numerical anal-
ysis. Box 3-3 explains how I have chosen to handle atomic weight
intervals in the latest periodic table of the elements.

CHAPTER 9 EXAMPLE PAGE 193

Features
Topics are introduced and illustrated with concrete, interesting
A B C D E F
examples. In addition to their pedagogic value, Chapter Open- 1 Thallium azide equilibria
ers, Boxes, Demonstrations, and Color Plates are intended to 2
_ _
1. Estimate values of pC = –log[C] for N3 and OH in cells B6 and B7
help lighten the load of a very dense subject. Chapter Openers 3 2. Use Solver to adjust the values of pC to minimize the sum in cell F8

show the relevance of analytical chemistry to the real world and 4

5 Species pC C (= 10^-pC) Mass and charge balances bi
to other disciplines of science. I can’t come to your classroom 6 N3
_
2 0.01 C6 = 10^-B6
_
b1 = 0 = [Tl+] – [N3 ] – [HN3] = 1.19E-02
to present Chemical Demonstrations, but I can tell you about 7 OH
_
4 0.0001 C7 = 10^-B7
_ _
b2 = 0 = [Tl+] + [H+] – [N3 ] – [OH ] = 1.18E-02
some of my favorites and show how they look with the Color 8 Tl+ 0.021877616 C8 = D12/C6 ⌺bi2 = 2.80E-04

Plates located near the center of the book. Boxes discuss inter- 9 HN3 4.46684E-08 C9 = D13*C6/C7 F6 = C8-C6-C9
10 H+ 1E-10 C10 = D14/C7 F7 = C8+C10-C6-C7
esting topics related to what you are studying or amplify points
11 F8 = F6^2+F7^2
in the text. 12 pKsp = 3.66 Ksp = 0.000218776 = 10^-B12
13 pKb = 9.35 Kb = 4.46684E-10 = 10^-B13
14 pKw = 14.00 KW = 1E-14 = 10^-B14
Problem Solving
Nobody can do your learning for you. The two most important FIGURE 8-9 Thallium 2
azide solubility spreadsheet without activity coefficients.
2
ways to master this course are to work problems and to gain expe- Initial estimates pN 3 5 2 and pOH 5 4 appear in cells B6 and B7. From these two
numbers, the spreadsheet computes concentrations in cells C6 : C10. Solver then
rience in the laboratory. Worked Examples are a principal peda-
varies pN23 and pOH2 in cells B6 and B7 until the charge and mass balances in cell
gogic tool to teach problem solving and to illustrate how to apply F8 are satisfi ed.
what you have just read. Each worked example ends with a Test
Yourself question that you are encouraged to answer to apply what
you learned in the example. There are Exercises and Problems at the end of each chapter. Exer-
cises are the minimum set of problems that apply most major concepts of each chapter. Please
struggle mightily with an Exercise before consulting the solution at the back of the book. Prob-
lems at the end of the chapter cover the entire content of the book. Short Answers are at the
back of the book and complete solutions appear in the Solutions Manual.
Spreadsheets are indispensable for science and engineering and uses far beyond this
course. You can cover this book without using spreadsheets, but you will never regret taking
the time to learn to use them. A few of the powerful features of Microsoft Excel are described
as they are needed, including graphing in Chapters 2 and 4, statistical functions and regression
in Chapter 4, solving equations with Goal Seek, Solver, and circular definitions in Chapters 7,
8, 13, and 19, and some matrix operations in Chapter 19. The text teaches you how to con-
struct spreadsheets to simulate many types of titrations, to solve chemical equilibrium prob-
lems, and to simulate chromatographic separations.

Other Features of This Book

Terms to Understand Essential vocabulary, highlighted in bold in the text, is collected at
the end of the chapter. Other unfamiliar or new terms are italic in the text.
Glossary Bold vocabulary terms and many of the italic terms are defined in the glossary.
Appendixes Tables of solubility products, acid dissociation constants, redox potentials,
and formation constants appear at the back of the book. You will also find discussions of
logarithms and exponents, propagation of error, analysis of variance, balancing redox equa-
tions, normality, analytical standards, and a little bit about DNA.
Notes and References Citations in the chapters appear at the end of the book.
Inside Cover Here is your trusty periodic table, as well as tables of physical constants and
other information.

Preface xvii
 Media and Supplements
The Solutions Manual for Quantitative Chemical Analysis contains complete solutions to
all problems.
New Clicker Questions allow instructors to integrate active learning in the classroom
and to assess students’ understanding of key concepts during lectures. Available in Microsoft
Word and PowerPoint (PPT).
New Lecture PowerPoints have been developed to minimize preparation time for new
users of the book. These files offer suggested lectures including key illustrations and sum-
maries that instructors can adapt to their teaching styles.
New Test Bank offers questions in editable Microsoft Word format.
Premium WebAssign with e-Book www.webassign.com features time-tested, secure,
online environment already used by millions of students worldwide. Featuring algorithmic
problem generation, students receive homework problems containing unique values for com-
putation, encouraging them to work out the problems on their own. Additionally, there is
complete access to the e-Book, from a live table of contents.
Sapling Learning with e-Book www.sapling.com provides highly effective interactive
homework and instruction that improve student learning outcomes for the problem-solving
disciplines. Sapling Learning offers an enjoyable teaching and effective learning experience
that is distinctive in three important ways: (1) ease of use: Sapling Learning’s easy-to-use
interface keeps students engaged in problem-solving, not struggling with the software; (2)
targeted instructional content: Sapling Learning increases student engagement and compre-
hension by delivering immediate feedback and targeted instructional content; (3) unsurpassed
service and support: Sapling Learning makes teaching more enjoyable by providing a dedi-
cated Masters- and Ph.D.-level colleague to service instructors’ unique needs throughout the
course, including content customization.
The student website www.whfreeman.com/qca has directions for experiments which
may be reproduced for your use. You will also find lists of experiments from the Journal of
Chemical Education. Supplementary topics at the website include spreadsheets for precipi-
tation and redox titrations, discussion of microequilibrium constants, a spreadsheet simula-
tion of gradient liquid chromatography, and Fourier transformation of an interferogram into
an infrared spectrum. You will also find 24 selected Excel spreadsheets from the textbook
ready to use at the student website.
The instructors’ website, www.whfreeman.com/qca, has all artwork and tables from
the book in preformatted PowerPoint slides.

The People
My wife Sally works on every aspect of this book and the Solutions Manual. She contributes
mightily to whatever clarity and accuracy we have achieved.
Solutions to problems and exercises were meticulously checked by Heather Audesirk, a
graduate student at Caltech, and by Julia Lee, a senior at Harvey Mudd College.
A book of this size and complexity is the work of many people. Brittany Murphy, Anna
Bristow, and Lauren Schultz provided editorial and market guidance. Jennifer Carey was the
Project Editor responsible for making sure that all pieces of this book fell into the right place.
Marjorie Anderson attended to the challenging details of copyediting. Photo research and
permissions were ably handled by Cecilia Varas and Richard Fox. Matthew McAdams,
Janice Donnola, and Tracey Kuehn coordinated the illustration program. Anna Skiba-Crafts
was the courageous proofreader.

In Closing
This book is dedicated to the students who use it, who occasionally smile when they read
it, who gain new insight, and who feel satisfaction after struggling to solve a problem. I
have been successful if this book helps you develop critical, independent reasoning that
you can apply to new problems in or out of chemistry. I truly relish your comments, criti-
cisms, suggestions, and corrections. Please address correspondence to me at the Chemis-
try Division (Mail Stop 6303), Research Department, Michelson Laboratory, China Lake,
CA 93555.

Dan Harris
March 2015

xviii Preface
Another random document with
no related content on Scribd:
in good condition for their government owner—His “discovery”
that the states, political entities, made the Constitution of
America, the nation of men—Story of America (from May 29,
1787, to July, 1917) being a sealed book to him, he does not
know that our Constitution is both federal and national—
Supreme Court, in early days and in 1907, and Webster and
Lincoln tell him his mistake—Not knowing the decision of
Gettysburg, recorded at Appomattox, he chooses between Lord
North of 1775 and Calhoun and summons the latter to prove that
the American people did not make their Constitution and its
grant of enumerated power to interfere with their individual
freedom—Jefferson, Pendleton, Webster and many other
Americans correct Sheppard’s error of fact—As the American
people of 1776 accomplished their successful Revolution
against government, may it not be the thought of Sheppard and
other Tories that the Eighteenth Amendment has been
established by a successful revolution of government against
the people—Marshall again tells us of the American day when
the legal necessity “was felt and acknowledged by all,” that
every power to interfere with human liberty must be derived from
the people in their “conventions”—Acting on the Congress
proposal of 1917, governments of state citizens command the
American citizen and create a new government power to
interfere with his individual liberty—But no statesman has yet
told us how or when, prior to 1917, we became “subjects.”
XIX. Are We Citizens? Page 298
Hamilton thinks it a prodigy that Americans, in “conventions,”
voluntarily constitute the enumerated First Article government
powers to interfere with their individual liberty—Marshall, in
Supreme Court, declares “conventions” to be the only manner in
which they can act “safely, wisely and effectively” in constituting
government of themselves, by making such grants—When
proposed 1917 first new grant of that kind is supposedly made,
American people and their “conventions” are completely ignored
—The proposers have a Fifth Article which does not mention
“conventions”—The proposers have the old Tory concept, that
the people are the assets of the state and that government is the
state—Still trying to find out how and when we became
“subjects,” we expect to get information from the litigations of
1920—We expect great counsel, on one side, to urge the facts
we know—We fear that other great counsel will urge, in reply,
some fact or facts which we have not been able to ascertain—
We are certain that there is no Eighteenth Amendment, if the
facts we have learned are all the facts—That we may listen
intelligently to all the great counsel, we review some of the facts
we have learned.
XX. Lest We Forget Page 307
“The important distinction so well understood in America,
between a constitution established by the people and
unalterable by the government and a law established by the
government and alterable by the government”—Our first glance
at briefs of 1920 gives us hope that some modern leaders have
acquired the knowledge of Hamilton and his generation—We
find, in one brief, in Marshall’s words, the Supreme Court
statement of the fact that “conventions” of the people, not states
or their governments, made the Constitution with its First Article
grants of power to interfere with human liberty—But this brief, to
our amazement, is that of the foremost champion of the only
other grant of that kind, the Eighteenth Amendment, a grant
made entirely by government to government—In 1920, seven
litigations argued and reported under the one title “The National
Prohibition Cases”—Distinguished counsel appear for many
clients, for the claimed omnipotent Parliament of America, for
the American government which we used to know as our
supreme government, for a few state governments who did not
wish to be part of the omnipotent Parliament, for those engaged
in the lawful business of manufacturing, etc., the commodities
named in the Eighteenth Amendment—Like the human right to
breathe, such manufacture, etc., was not the privilege of a
citizen—Both rights are among the human rights men have
before they create nations and give governments power to
interfere with some or all of their human rights—Citizens of
America, giving their only American government its enumerated
powers, gave it no power to interfere with the human right
mentioned in the new Amendment—Human rights never are
privileges of citizens—Citizens establish government to protect
existing human rights—Only “subjects” get any rights or
privileges from government—All early Americans knew these
primal truths—Neither the French aristocrats, before French
Revolution, nor Tories of 1776 in England or America knew them
—Eighteenth Amendment Tories do not know them—Madison
(in 1789) and Supreme Court (in 1890) knew that commodities
named in new Amendment are among those in which a human
right “of traffic exists”—In litigations of 1920, no counsel appear
on behalf of the human rights of American citizens—But we
know that no decision of our own Supreme Court, established to
secure our human rights, although the decision may settle
disputes between other litigants, can change us from “citizens”
into “subjects.”
XXI. Briefs Ignore the American Page 325
Citizen
No counsel knows all are discussing whether Americans, twelve
years after 1776, voluntarily became “subjects”—Common
concept of all that Fifth Article a “grant” of power to state
governments (of state citizens) making them attorneys-in-fact for
citizens of America—Discussion entirely as to extent of power
“granted”—Eighteenth Amendment concept that Fifth Article
“grant” made some governments of state citizens a supreme
American Parliament, unrestrained master of every human right
of all American citizens—Opposing concept that the Fifth Article
“grant” made those state governments a Parliament whose one
limit is that it cannot interfere with the sovereignty of any political
entity which is a state—Both concepts ignore supremacy of
nation of men over federation of states—Both ignore dual nature
of “one national and federal Constitution”—Both ignore
“conventions” in Seventh and Fifth Articles as the citizens of the
American nation—Both ignore that each state “legislature” is
attorney-in-fact for the citizens of its own state and that no
legislatures are (except Congress in enumerated matters)
attorneys-in-fact for the citizens of America in any matter—Our
facts, brought from our education with the early Americans, all
ignored by all counsel in the litigations—The Virginia Convention
itself and Lee, Pinckney, Hamilton, Madison, Wilson, Iredell and
others state what all counsel of 1920 entirely ignore.
XXII. No Challenge to the Tory Page 335
Concept
Eighteenth Amendment rests on imaginary Fifth Article “grant”
making the state governments of state citizens attorneys-in-fact
for the citizens of America, empowered to give away all human
rights of the citizens of America—“Grant” assumed in every brief
—No brief recognizes that one supposed “grantee” is supposed
“grantor”—Or that each of two supposed “grantees” was a
competent maker of Articles (as proposed Articles were
respectively federal or national) before and when the
“conventions” made the Fifth Article—Or that Philadelphia
Convention knew and held “conventions” existing ability
competent to make any Article and state legislatures, existing
ability incompetent ever to make Articles like First Article or
Eighteenth Amendment—Or that Tenth Amendment declares no
power given to state “legislatures,” while all ability to make
national Articles “reserved” to “conventions” of “the people” of
America—No brief challenges sheer assumption of Fifth Article
“grant” or supports assumption by any fact—Every brief, for or
against Amendment, is based on the sheer assumption—No
brief knows that enumerated powers of only American
government to interfere with human freedom can be changed by
no one save the citizens of America themselves in their
“conventions”—Madison’s tribute to these “conventions” in which
“free inhabitants” constitute new government power over
themselves—Hamilton explains great danger to human liberty if
“legislatures” or permanent government bodies could create
such new government power—That knowledge of his generation
confirmed by story of government-made supposed Eighteenth
Amendment—Our gratitude to that generation of men who
(1776) made it and (1788) left it impossible that governments
could create new government power to interfere with American
human liberty—Our regret that modern leaders have not known
this great and immutable protection to American liberty.
XXIII. The Challenges That Failed Page 350
Supreme Court wisely writes no opinion in “National Prohibition
Cases”—In each of four numbered paragraphs, Court states its
own negation of one challenge made to new Amendment—All
four challenges are negatived in seventeen lines of statement—
First two challenges trifling and purely technical—Third
challenge based on rights of the citizens of some particular state
—Fourth challenge to “extent” of Fifth Article “grant” of power by
“conventions” to “conventions” and “legislatures”—This
challenge asserts “grant” which advocates of Eighteenth
Amendment must and cannot prove—Court negative amazingly
accurate—All counsel have argued incessantly about “extent” of
power “granted” by Fifth Article—Court negatives in statement
which speaks of power “reserved” in Fifth Article—Concept of
“grant” disappears—Court knows what “conventions” knew,
when they made Fifth Article, when they insisted on Tenth
Amendment Declaration expressly stating the distinct reservees
of the two existing powers “reserved” in Fifth Article—Supreme
Court of Marshall’s day knows it and Supreme Court of 1907
knows it—“Citizen or Subject?”—Eighteenth Amendment
answers “Subject”—Real Constitution answers
“Citizen”—“Conventions” insisted on plain statement of correct
answer—Counsel of 1920 do not know it—Their four challenges
make plain that fact—All challenges based on error that
governments of state citizens are attorneys-in-fact for citizens of
America—In Virginia Convention and in Supreme Court,
Marshall explains that powers of state governments “proceed
not from the people of America” but from the citizens of each
respective state—No counsel of 1920 knows this important fact.
XXIV. Governments Claim Americans as Page 371
Subjects
Patrick Henry, opposing Constitution in the “conventions,” knows
that it takes power from the state legislatures and gives them no
power—All modern leaders “know” that it gives those
legislatures great power as attorneys-in-fact for the citizens of
America—Many modern leaders “know” that it makes those
legislatures an omnipotent Parliament over the citizens of
America—No modern leaders remember 1781 and 1787
existing ability of the state legislatures to make federal Articles
or Articles not creating government power to interfere with
human liberty—Common modern concept that Fifth Article is
“grant” to these “legislatures” and to the very “conventions”
which made the Fifth Article—Leading brief, against
Amendment, more than fifty times admits or asserts this
imaginary and remarkable “grant”—Some extraordinary
concepts of our American institutions in briefs—In a famous
opinion, Marshall explains a fact and on it bases the entire
decision of the Supreme Court—The fact itself is that the
Constitution granted no power of any kind to the state
legislatures—No brief knows or urges this fact or any of the facts
we learned in the “conventions,” the facts on which we base our
challenge to the Eighteenth Amendment concept that we are
“subjects”—Briefs for the Amendment examined to find out why
we are supposed to be “subjects”—Amazing claim that, when
governments alone change the national part of the Constitution,
Supreme Court has no power even to consider whether
governments in America can make a change in the enumerated
powers given to their own government by the citizens of America
—Remarkable Tory concept that the number of Senators from
each state is the only thing in America immune from government
invasion, if enough governments combine—Indignation of
American citizen changes to mirth when he realizes this concept
to be only basis of thought that he is a “subject” or that there is
an Eighteenth Amendment—American citizen, seeking to find (in
the briefs for the Amendment) what happened, between 1907
and 1917, to make him a “subject,” startled to hear the answer,
“Nothing”—Citizen’s amusement increased on learning, in same
briefs, that whole American people, in Constitution which
expressly declares it gives no power to state governments,
made those governments of state citizens irrevocable and
omnipotent attorneys-in-fact for the citizens of America—
Amusement increased by finding that main champion of Tory
concept quotes Marshall’s Supreme Court story of the making of
the Constitution, but omits, from the quotation, the paragraph in
which Marshall points out that everyone knew why the
“legislatures” could not make and only the “conventions” could
make the national First Article, with its grant of enumerated
power to interfere with human liberty—Curiosity added to mirth
on finding this brief echo Madison’s own knowledge that his Fifth
Article contains nothing but “procedural provisions,” while brief
bases its entire contention on mere assertion that Fifth Article is
greatest grant of power ever made by free men to government.
XXV. Citizen or “Eighteenth Page 397
Amendment”?
Congress is only legislature with any power of attorney from the
citizens of America—At very beginning and very end of original
Constitution, citizens of America expressly so state—All briefs of
1920 based on asserted assumption denying those two
statements and insisting Fifth Article is “grant” to governments of
state citizens—Briefs for new Amendment assert “grant” made
governments of state citizens omnipotent master of everything in
America (including all human rights) save number of Senators
from each state—On this Tory concept depends entirely
existence of Eighteenth Amendment—Tory concept being
absolute myth, Amendment disappears—Amusing to find Tory
briefs for Amendment with American citations and quotations
which annihilate Tory concept—Unconscious humor of Wheeler
surpasses “Comic Blackstone”—Tory legions, fighting under
crescent of Mohammet, claim to be American and Christian
crusaders—Americans would have remained “subjects” if
Parliament, passing the Stamp Act, had said: “You subjects
must obey this command we make but, making it, we do not
legislate”—“Statement” that citizens of America universally
demanded this sole Amendment which attempts to change the
First Article enumerated powers—“Proof” that 4742 Tory
members of governments of state citizens said “Yes” to the
change—Jefferson and Madison tell us that concentration of all
power in legislatures “is precisely the definition of despotic
government,” that 173 “despots would surely be as oppressive
as one,” and that “an elective despotism was not the
government we fought for”—Calhoun contended one state might
defy supreme will of citizens of America—Tories for Amendment
go far beyond doctrine finally repudiated by Gettysburg—On
Tory concept that we are “subjects” of omnipotent government,
assert that some governments of state citizens may dictate, in
all matters of human right, what the citizens of America may and
may not do—Echo from “conventions” which made Fifth Article,
“How comes it, sir, that these state governments dictate to their
superiors, to the majesty of the people?”
XXVI. The American Citizen Will Remain Page 416
Supreme Court holds American people, “for most important
purposes,” chose to be one nation, with only one government of
the First Article enumerated powers to interfere with human
liberty—America, the nation of men, and United States, the
subordinate federation of states—Tories for new Amendment
must prove that American people, as one “important” purpose,
meant that governments of state citizens could interfere with
every human right of American citizens—Reserved rights and
powers of American citizens are entirely at their own direct
disposal, for exercise or grant, “despite their legislatures,
whether representing the states or the federal government”—
American citizen must know this of his own knowledge or his
human freedom will disappear—Emmett and Webster and their
generation knew it—Madison writes Fifth Article and states
exactly what it is to the “conventions” which made it—Hughes
unable to begin his Tory argument for new Amendment without
adding to that Madison statement what Madison pointedly did
not say—Senate now about to repeat 1917 blunder that
governments of state citizens have aught to do with altering the
national part of the American Constitution, which part is within
the exclusive control of the citizens of America themselves
—“Conventions” are the people—“Legislatures” are
governments—“Citizen or Subject?”—Supreme Court answer
certain—Court’s history and traditions show American concept
of Hamilton that this Court bulwark of American citizen against
government usurpation of power to interfere with human liberty
—Webster forecast Court decision on new and Tory
Amendment, answering “Citizen or Subject?”—All Americans
once knew same correct answer to same question by Pendleton
in Virginia Convention of 1788, “Who but the people can
delegate power? What have the state governments to do with
it?”
APPENDICES
I. The Original Constitution of the Page 445
United States
II. The Resolution Which Proposed Page 458
the Constitution to the
Conventions of the People of
America
III. The First Seventeen Amendments Page 460
to the Constitution
IV. The Alleged Eighteenth Page 465
Amendment
V. The Nineteenth Amendment Page 466
CITIZEN OR SUBJECT?
 CHAPTER I
SUBJECTS BECOME CITIZENS

The average American of this generation does not understand

what it means to be a citizen of America. He does not know the
relation of such a citizen to all governments in America. He does not
know the relations of those governments to one another. If this
ignorance should continue, the citizen of America would disappear.
The American would become again a subject, as he was when the
year 1776 opened.
The supposed Eighteenth Amendment is not in the Constitution
unless the American already is a subject.
It is vital to every individual interest of the average American that
he should know these things which he does not know. Happily for
him, his ignorance is not as that of the public leaders of his
generation. Their concept of the American and his relation to
governments in America is one which contradicts the most definitely
settled and clearly stated American law. On the other hand, the
average American merely has a mind which is a blank page in these
matters. As a result, it is the greatest danger to his individual interest
that their concept largely guides his attitude in public affairs of the
utmost moment to him.
The Americans of an earlier generation, who created the American
nation of men and all governments in America, accurately knew the
status of the American citizen and his relation to all governments.
Their accurate knowledge was an insistent thing which guided their
every act as a people in the period between 1775 and 1790, in which
latter year the last of the Americans became citizens of America.
Their knowledge came to them from their own personal experience
in those fifteen years. They were a people, born subjects of
government, who died citizens of a great nation and whose every
government, in America, was their servant. This great miracle they
themselves had wrought in the fifteen years between 1775 and
1790. Their greatest achievement, as the discerning mind has
always realized, is what they did in the last four of those momentous
years. They brought to its doing their valuable experience and
training of the previous eleven years. That is why they succeeded,
so far as human effort can secure human liberty by means of written
constitutions of government, in securing to themselves and their
posterity the utmost measure of protected enjoyment of human life
and happiness. That we, their posterity, may keep their legacy intact
and transmit it to the generations to come, it is necessary that we,
the average Americans, should share somewhat with them their
amazingly accurate knowledge of the simple but vital facts which
enabled them to create a nation and, by its American Constitution, to
secure to themselves, its citizens, protected enjoyment of life, liberty
and happiness.
When they were actually engaged in this work of creation, it was
truthfully said of them that “The American people are better
acquainted with the science of government than any other people in
the world.” For over a hundred years the history of America attested
the truth of that statement. As they were a simple people, their
knowledge of the science of government was derived from their
accurate understanding of a few simple facts. It is a certainty that we
can keep their legacy by learning those same facts. Let us quickly
learn them. The accurate knowledge of them may best be acquired
by briefly living again, with those simple Americans of an earlier
generation, through their days from 1775 to 1790.
The individual Americans of that generation were all born subjects
of the British government. We do not understand the meaning of that
statement until we accurately grasp the vital distinction between a
“subject” of a government and a “citizen” of a nation.
It is hardly necessary to point out, but it is amazingly important to
remember, that a “subject,” as well as a “citizen,” is first of all a
human being, created by an omnipotent Creator and endowed with
human rights. All would be well with the world, if each human being
always accurately knew the difference between right and wrong and
if his accurate knowledge invariably controlled his exercise of his
human freedom of will. In that case, no human government would be
needed to prescribe and to enforce rules of personal conduct for the
individual. As such is not the case, human government must exist.
Its sole reason for existence, therefore, is that it may prescribe and
enforce rules for those whom it can compel to obey its commands
and that it may thus secure the utmost measure of protected
enjoyment of human rights for those human beings whose
government it is.
Time does not permit and necessity does not require that we dwell
upon the various types of government which have existed or which
have been created supposedly to meet this human need. It is
sufficient to grasp the simple and important fact that government
ability to say what men may or may not do, in any matter which is
exercise of human freedom, is the very essence of government.
Where a government has no ability of that kind, except what the men
of its nation grant to it, where those men limit and determine the
extent of that ability in their government, the men themselves are
citizens. Where a government claims or exercises any ability of that
kind, and has not received the grant of it directly from the men of the
nation, where a government claims or exercises any ability of that
kind, without any grant of it, or by grant from government to
government, the men of that nation are subjects.
In the year 1775, under the British law, the Parliament at
Westminster claimed the unqualified right to determine in what
matters and to what extent laws should be made which would
interfere with individual freedom. From such decision of the
legislative part of the British Government there was no appeal save
by force or revolution. For this reason, that every human being under
that Government must submit to any interference with individual
freedom commanded by that Legislature, all British human beings
were “subjects.” And, as all Americans were then under that British
Government, all Americans were then “subjects.” Such was their
legal status under the so-called British Constitution. Curiously
enough, however, until a comparatively short time prior to 1775, such
had not been the actual status of the Americans. In this sharp
contrast between their legal and their actual status, there will be
found both the cause of their Revolution and the source of their great
and accurate knowledge of the sound principles of republican
government which they later made the fundamental law of America.
From the day their ancestors had first been British colonists in
America their legal status had been that of subjects of the British
Government. But, so long as they remained merely a few widely
scattered sets of human beings in a new world, struggling to get a
bare existence from day to day, they offered no temptation to the
omnipotent British Government to oppress them, its subjects. They
still had to show the signs of acquiring that community wealth which
has always been the temptation of government to unjust exaction
from the human beings it governs. For that reason, their legal
government concerned itself very little about them or their welfare. It
thus became their necessity to govern themselves for all the
purposes for which they locally needed government as security to
their individual welfare.
Only thirteen years after the first permanent English settlement in
Virginia, “Sir George Yeardley, then the Governor of the colony, in
1619 called a general assembly, composed of representatives from
the various plantations in the colony, and permitted them to assume
and exercise the high functions of legislation. Thus was formed and
established the first representative legislature that ever sat in
America. And this example of a domestic parliament, to regulate all
the internal concerns of the country, was never lost sight of, but was
ever afterwards cherished [until 1917] throughout America, as the
dearest birthright of freemen.” (1 Ell. Deb. 22.)
“On the 11th of November, 1620, those humble but fearless
adventurers, the Plymouth colonists, before their landing, drew up
and signed an original compact, in which, after acknowledging
themselves subjects of the crown of England, they proceed to
declare: ‘Having undertaken, for the glory of God, and the
advancement of the Christian faith, and the honor of our king and
country, a voyage to plant the first colony in the northern parts of
Virginia, we do, by these presents, solemnly and mutually, in the
presence of God and of one another, covenant and combine
ourselves together into a civil body politic, for our better ordering and
preservation, and furtherance of the ends aforesaid. And by virtue
hereof do enact, constitute, and frame, such just and equal laws,
ordinances, acts, constitutions, and officers, from time to time, as
shall be thought most meet and convenient for the general good of
the colony; unto which we promise all due submission and
obedience.’ This is the whole of the compact, and it was signed by
forty-one persons.
“It is, in its very essence, a pure democracy; and, in pursuance of
it, the colonists proceeded soon afterwards to organize the colonial
government, under the name of the Colony of New Plymouth, to
appoint a Governor and other officers and to enact laws. The
Governor was chosen annually by the freemen, and had at first one
assistant to aid him in the discharge of his trust. Four others were
soon afterwards added, and finally the number was increased to
seven. The supreme legislative power resided in, and was exercised
by, the whole body of the male inhabitants, every freeman, who was
a member of the church, being admitted to vote in all public affairs.
The number of settlements having increased, and being at a
considerable distance from each other, a house of representatives
was established in 1639, the members of which, as well as all other
officers, were annually chosen.” (1 Ell. Deb. 25.)
These are two examples typical of the way in which the English
colonists, for the first hundred years, largely governed themselves by
legislators chosen from among themselves. In this manner, while
legally “subjects” of their European government, these Americans
were actually “citizens” of their respective communities, actually
governed in their individual lives and liberties by governments which
derived all their powers of government from these “citizens.” In this
manner, through the best teacher in the world, personal experience,
they learned the vital difference between the relation of “subject” and
“citizen” to governments. Later, the echo of that education was heard
from Lincoln when he pleaded that government of the people, by the
people and for them should not perish from the earth.
As early as 1754 these Americans began to feel the first real
burden of their legal status as “subjects.” Their community wealth
was beginning to attract the attention of the world. As a result, the
legal Government awoke to the fact of their existence and of its own
omnipotent ability to levy upon that wealth. The Americans, for more
than a century educated in actual self-government, quickly showed
the result of that education to the accurate knowledge that no
government can have any just power except by the consent or grant
of those to be governed by the exercise of such power. As far back
as 1754, deputies of the various American colonies, where human
beings had educated themselves to be free men, assembled at
Albany in an endeavor to propose some compromise by which the
American people would be enabled to preserve their human freedom
against unjust interference by the Westminster Legislature. We are
all familiar with the failure of that endeavor. We are all familiar with
the successive steps of the continuing struggle between “subjects,”
educated to be “citizens,” and an omnipotent government, unshaken
in its purpose to make their actual status the same as their legal one.
When the year 1776 dawned, these Americans were still
“subjects” under the law of the British Empire. They were, however,
“subjects” in open rebellion against their government, justifying their
rebellion on the basic American legal principle that every just power,
even of a lawful government, must be derived from the consent or
grant of the human beings themselves who are to be governed. On
the memorable day in July of that year, despairing of any success in
getting the British Government to recognize that basic principle, and
asserting, for the first time in history, that they themselves were
collectively the possessors of the supreme human will in and for
America, they enacted the immortal Statute which we know as the
Declaration of Independence.
The Declaration of Independence, which was the first
political act of the American people in their independent
sovereign capacity, lays the foundation of our national
existence upon this broad proposition: “That all men are
created equal; that they are endowed by their Creator with
certain inalienable rights; that among these are life, liberty,
and the pursuit of happiness.” (Justice Bradley’s opinion in
Slaughter House Cases, 16 Wall. 36, at page 115.)
 In this Statute, the American people clearly stated and definitely
settled for all time the basic legal principle on which rests the validity
of every constitutional article or statute law, which either directly
interferes or vests ability in governments to interfere with an
American in the exercise of his human freedom. There is nothing
vague or ambiguous in their statement. The legal principle, so clearly
stated and so definitely settled, is that no government in America can
have any just power of direct interference with individual freedom
unless such power be derived by direct grant from the Americans to
be governed by the exercise of that power.
That Statute has never been repealed. The Americans of that
generation, throughout all the momentous political battles of the next
thirteen years, when they were making and unmaking nations and
creating a federation of nations, and later subordinating it to a union
of human beings, never failed to obey that Statute and to act in strict
conformity to its basic American principle.
From the moment when that Statute was enacted by the supreme
will in America, every American ceased forever to be a “subject” of
any government or governments in the world. It was not until 1917
that any government or governments dared to act as if the American
were still a “subject.”
In that summer of 1776, as the Americans were engaged with their
former Government in a bitter and protracted war, they had little time
or thought to give, as one people, to the constitution of a government
best designed to secure to themselves the utmost possible measure
of protected enjoyment of individual human freedom. In their
rebellion, they had delegated the management of their common
interests to a committee of deputies from each former colony, which
committee was called the Congress. By the declared supreme will of
the whole American people, the Americans in each former colony
now constituted an independent nation, whose human members
were now the “citizens” of that nation. Under the declared basic
American legal principle, it was imperative that any government
should get its every valid power from its own citizens. Knowing this,
the Congress, almost immediately after the Declaration of July, made
the formal suggestion to the citizens in each nation that they
constitute a government for themselves and that they grant to such
government ability to interfere with their own human freedom in such
matters and to such extent as they deemed wise. The manner in
which the citizens of each nation acted upon this suggestion should
have stamped itself so irrevocably upon the mind of America as
never to have been forgotten by any later generation of Americans.
The citizens of those nations were of the “people who were better
acquainted with the science of government than any other people in
the world.” In each nation they were creating the very essence of
security for a free people, namely, a government with limited ability
to interfere with individual freedom, in some matters, so as to secure
the greatest possible protected enjoyment of human liberty. They
knew, as only human beings could know who were then offering their
very lives to uphold the basic law of America, that such ability could
never be validly given to any government by government itself,
acting in any manner, but only by direct action and grant of those
later to be governed by the exercise of that ability. What method did
those citizens, so thoroughly educated in the basic principles of
republican government, employ to secure the direct action of the
human beings themselves in giving that ability of that kind to their
respective governments? They acted upon the suggestion from the
Congress of 1776, as Marshall later expressed it from the Bench of
the Supreme Court, “in the only manner in which they can act safely,
effectively and wisely on such a subject, by assembling in
convention” in their respective states. Long before Marshall voiced
judicial approval of this American method of direct action by the
people themselves, in matters in which only the people themselves
can validly act at all, Madison, in the famous Virginia convention of
1788, paid his tribute to these conventions of the people in each of
the thirteen nations. This was the tribute of Madison: “Mr. Chairman,
nothing has excited more admiration in the world than the manner in
which free governments have been established in America; for it was
the first instance, from the creation of the world to the American
Revolution, that free inhabitants have been seen deliberating on a
form of government, and selecting such of their citizens as
possessed their confidence, to determine upon and give effect to it.”
(3 Ell. Deb. 616.)
 Later herein there will be occasion to speak at greater length of
this American method of direct action by the people themselves,
through the deliberative conventions of deputies chosen by the
people and from the people for that one purpose, giving to
governments a limited ability to interfere with individual freedom. At
this point, it is sufficient to say that, since 1789 and until 1917, no
government in America ever claimed to have acquired ability of that
kind except through the action of such a convention or conventions
or through the direct voting of its citizens themselves for or against
the grant of such ability.
If we again turn our minds upon those later days of 1776, we find
that the Americans, through the direct action of the people in each
independent nation, had become respectively citizens of what we
now know as their respective states, each of which was then a free
nation. Those thirteen nations were then allied in war. There did not
yet exist even that political entity, later created and known as a
federation of those nations. At that time and until quite some years
after the Revolution had ended, there was no such thing as a
“citizen” of America, because the America we know, the organized
human membership society which is the American nation, did not yet
exist. At that time and until the American nation did actually exist, as
a political entity, there was no government in the world and no
collection of governments in the world, which, on any subject or to
any extent, could interfere generally with the individual freedom of
Americans, as Americans. In each of the thirteen American nations,
the citizens of that nation had vested their own government with
some ability of that kind.
At this point, it is well to digress for a moment in order that we may
well understand that in none of these thirteen nations did its citizens
vest in its government an unlimited ability to interfere with individual
freedom. All the citizens of those respective nations were then
battling with a mighty Government which claimed such unlimited
ability over all of them, as subjects, and they were battling to
establish forever in America the basic doctrine that no government of
free men could ever have unlimited ability of that kind. In each of the
thirteen nations, its citizens vested its government with ability of that
kind only to a limited extent. They did this in strict conformity to
republican principles.
For the many who do not know, it is well to state clearly the
distinction between a pure democracy and a republic. In both, the
human beings constitute the nation or the state and are its citizens.
In both, the citizens themselves limit the matters and the extent in
which they shall be governed at all in restraint of their individual
freedom. In both, therefore, it is accurate and truthful to state that the
people govern themselves. The actual difference lies in one fact. In a
democracy the people themselves assemble and themselves enact
each specific rule of conduct or law interfering with individual
freedom. In a republic, it is always possible that the citizens may
assemble, as in a pure democracy, and enact any specific rule of
conduct or law. But, in a republic, its citizens generally prefer to act,
in such matters, through attorneys in fact or representatives, chosen
by themselves for the special purpose of exercising a wise discretion
in making such laws. In a true republic, however, where the citizens
are to remain free men, they secure to themselves absolute control
of their representative lawmakers through two most effective means.
In the first place, they ordain that their attorneys in fact for the
purpose of law-making, generally called their legislators, shall be
selected by themselves from time to time, at comparatively short
intervals. This precaution enables the people, through new attorneys
in fact, quickly to repeal a law of which they do not approve. In the
second place, the people, in constituting their government, limit the
law-making ability of these temporary attorneys in fact or legislators.
This is the most important fact in a free republic. Later herein there
will be explained the marvelous and effective manner in which this
particular security for human freedom was later achieved by the
citizens of the Republic which we know as America, when they
constituted their government. At present, there is to be mentioned
the general method which the citizens of each of those thirteen
nations, in 1776, employed to achieve this particular security.
In each nation the citizens constituted a legislature to be their only
attorney in fact for the purpose of making valid laws. In this
legislative department they did not vest enumerated powers to