| Quantitative Chemical Ne Seventh Edition io (OmariHydrogen] Periodic Table ‘Aomnie Number. 3 4 4a Li Be thm, |” Bey esutszt |oor ens 11 |12 + losr lnz4 e Na= Mg Botting point [2243 wo _| 3562 Melting point (k—— ] 1943 Ti Density at 300] 4-5, ‘aren3) Titanium Sorcrast 47.867 fi ‘inert gaunt | 3 asi Ses T= 47.867 £0001 [Afomlc masses from Pure Appl. Chem. 2003, 75, 1107) 4 5 6 7 8 Atomic mage te accurate foe I ast deciral place {less otherwise indicated & Fre Ral Ac Francium |” Radium | Actinium (zz) (25) (ez) F DE Sg [Rutherfordium| Dubrium | Seaborgiu (282) 268) 49 + [20 2 [24 +3 [22 +4 [23 5052 124 32 [2576423/26 123/27 23 ee Oa tee ead a ie area nw eee = Ki Cal Sem Tie Vie Crie:Mni= Fel Co Totssum |'ctsum, | Sentiom [rani | Yaredun [Gorin | Wargarase |" on | cob Pasa | Gan, [cota] Tataa” | Vai | SSeS ASSP | star [nano 37.4 (138 2 (39 3 (40 oe (41 ss AQ ee5002|43 7 [4d rseee|45 230 See eee ee eee bey arte lee ea low tesie eee eae tae b= Rb Sri@ Yee ZreNbe Mor Tc Ru Rh ‘utigum |"Sontim | vtvun |“Zrconn | osiom_|Noyederum|"Tectztion |"Euthosum |" Rhodium Eusien, | Seg | atm | icenum | aucun | Mayas) Tema | ater | asses ar2 55 4 (56 2 (S57 3 [72 os 173s [74 v05432/75 75424] 76 12346877 esas a eae la (ee octet (cere een ee lee Csi Bal Lal Hf Tap Osi Ir ‘asum [oun | tanto tation |“tansm | "tungsten s ial warty | waaeess | caeret | tae 87 + (88 2 [89 104 105 106 ‘commercial ithium compounds TB. Copten, .Z. Wang 4 ian, Anal Chem 1997, 69,4078] 58 34 (59 +34 [60 52 =< [80 fe Cel Pris Cea esel eal Sate Rosson Neri 90 « [94 154 192 6543 BO are tae = The, Pal U nema acne ‘Thor |Protetnin|“Urarunof the Elements ,J3 14 15 16 17 18 © Hel foros Hoium 60242 ee Ne} Neon 20.1707 36. 7/18ee ae Quantitative Chemical Analysis SEVENTH EDITION Daniel C. Harris Michelson Laboratory China Lake, CaliforniaD ; > c vo x Brief Contents The Analytical Process 1 Measurements Tools of the Trade Experimental Error Statistics aOR wR Quality Assurance and Calibration Methods on Chemical Equilibrium n Let the Titrations Begin 8 Activity and the Systematic Treatment of Equilibrium 9 Monoprotic Acid-Base Equilibria 10 Polyprotic Acid-Base Equilibria 11 Acid-Base Titrations 12 EDTA Titrations 13 Advanced Topics in Equilibrium 14 Fundamentals of Electrochemistry 15 Electrodes and Potentiometry 16 Redox Titrations 78 % 121 140 180 199 228 250 270 298 327 17 Electroanalytical Techniques 348 18 19 20 21 22 23 24 25 26 27 28 Fundamentals of Spectrophotometry Applications of Spectrophotometry Spectrophotometers Atomic Spectroscopy Mass Spectrometry Introduction to Analytical Separations Gas Chromatography High-Performance Liquid Chromatography Chromatographic Methods and Capillary Electrophoresis Gravimetric and Combustion Analysis Sample Pre 378 402 424 453 474 501 528 556 588 628Contents Pretace xiii 0 The Analytical Process 1 A Biosensor for Arsenic in the Environment 4-2. Confidence Intervals 7 4-3. Comparison of Means with Student’s ¢ 59 Box 4-1 Analytical Chemistry and the Law 63 4-4 Comparison of Standard Deviations 0-1 The Analytical Chemist's Job Bee rear cones 3 0-2. General Steps in a Chemical Analysis Tear cea aerial Dea ee Box 0-1 Constructing « Representative Sample 7 4. The Method of Least Squares a 48° Calibration Curves o Measurements Box 4-2 Using a Nonlinear Calibration Curve 71 Ultrasensitive Measurement of Atoms 4-9. A Spreadsheet for Least Squares a in a Vapor 1-1 SI Units 9 5 Quality Assurance and 1-2 Chemical Concentrations 12 Calibration Methods 78 1-3. Preparing Solutions ee 1-4 Stoichiometry Calculations 16 Prien 5-1 Basics of Quality Assurance 9 Box $-1 Control Charts 81 _2 ToolsoftheTrade 205.9 ene Validation 82 ‘The Smallest Balances Box 5-2. The Horwitz Trumpet: Variation 241 Safe, Ethical Handling of Chemicals and Waste 20 in Interlaboratory Precision 85 Box 2-1 Disposal of Chemical Waste 5-3 Standard Addition 8 22. The Lab Notebook 5-4. Internal Standards 90 2-3. Analytical Balance 2-4 Burets & Chemical Equilibrium % 2-5 Volumetric Flasks 2-6 Pipets and Syringes Chemical Equilibrium in the Environment aa Eenen 6-1 The Equilibrium Constant 97 28 Drying 6-2. Equilibrium and Thermodynamics 98 2.9. Calibration of Volumetric Glassware ag couality roduc ee 2-10 Introduction to Microsoft Excel Box 6-1 Solubility Is Governed by More 2-11 Graphing with Microsoft Excel ‘Than the Solubility Product tor Demonstratio fect 102 3 Experimental Error 39 04 Complex Ii ne Experimental Error 65 3-1. Significant Figures 3966 3-2. Significant Figures in Arithmetic 40 67 ceapspen 33° Types of Error 42 Fountain Box 3-1 Standard Reference Materials 43 3-4 Propagation of Uncertainty from Random Esror 44 Box 3-2 Propagation of Uncertainty in the Product x - x 48 3.5. Propagation of Uncertainty: Systematic Error 49 4 Statistics 53 iS Begin. Is My Red Blood Cell Count High Today? Evolution = 4-1 Gaussian Distribution 537-1 Titrations 121Box 7-1, Reagent Chemicals and Primary Standards 123 7-2. Titration Calculations 123 7-3. Spectrophotometric Titrations 126 7-4. The Precipitation Titration Curve 127 Titration of a Mixture 131 7-6 Calculating Titration Curves with a Spreadsheet 132 7-7 End-Point Detection 133 Demonstration 7-1 Fajans Titration 134 7-8 Efficiency in Experimental Design 134 8 Activity and the Systematic Treatment of Equilibrium 140 Hydrated Ions 8&1 The Effect of Ionic Strength on Solubility of Salts 141 Demonstration 8-1. Effect of lonie Strength on lon Dissociation 141 Box 8-1 Salts with fons of Charge = Do Not Fully Dissociate 143 8-2. Activity Coefficients 143 8.3. pH Revisited 147 8-4. Systematic Treatment of Equilibrium 147 Box 8-2. Calcium Carbonate Mass Balance in Rivers 150 8-5 Applying the Systematic Treatment of Equilibrium 150 9 Monoprotic Acid-Base Equilibria 158 Measuring pH Inside Cellular ‘Compartments 9-1 Strong Acids and Bases 159 Box 9-1 Concentrated HNO, Is Only Slightly Dissociated 159 9-2 Weak Acids and Bases 161 9-3. Weak-Acid Equilibria 162 Box 9-2. Dyeing Fabrics and the Fraction of Dissociation 6s Demonstration 9-1 Conductivity of Weak Electrolytes 165 9-4 Weak-Base Equilibria 166 9-5. Buffers 167 Box 9-3 Strong Plus Weak Reacts Completely 170 Demonstration 9-2 How Butfers Work 71 10 Polyprotic Acid-Base Equilibria__180 Proteins Are Polyprotic Acids and Bases 10-1 Diprotic Acids and Bases 181 Box 10-1 Successive Approximations 186 10-2 Diprotic Buffer 187 10-3. Polyprotic Acids and Bases 188 lye 10-4 Which Is the Principal Species? in 10-5 Fractional Composition Equations 191 10-6 Isoelectric and Isoionic PH 193 Box 10-2 Isoelectric Focusing 194 11 Acid-Base Titrations 199 Acid-Base Titration of a Protein 11-1 Titration of Strong Base with Strong Acid 200 11-2. Titration of Weak Acid with Strong Base 202 11-3. Titration of Weak Base with Strong Acid 205 11-4 Titrations in Diprotic Systems 206 11-5. Finding the End Point with a pH Electrode 208 Box 11-1 Alkalinity and Acidity 209 11-6 Finding the End Point with Indicators 212 Demonstration 11-1 Indicators and the Acidity of CO, a4 Box 11-2 What Does a Negative pH Mean? 214 Box 11-3 World Record Small Titration 216 11-7 Practical Notes 216 11-8. The Leveling Effect 216 11-9 Calculating Titration Curves with Spreadsheets 218 12_EDTA Titrations 228 Ton Channels in Cell Membranes 12-1 Metal-Chelate Complexes 229 12-2 EDTA 231 Box 12-1 Chelation Therapy and Thalassemia 232 12-3. EDTA Titration Curves 235 12-4 Do It with a Spreadsheet 237 12-5. Auxiliary Complexing Agents 238 Box 12-2 Metal fon Hydrolysis Decreases the Effective Formation Constant for EDTA Complexes 240 12-6 Metal Ton Indicators 241 Demonstration 12-1 Metal lon Indicator Color Changes m1 12-7 EDTA Titrati . 244 245 PR reno cf aR ON nce Plots WATERMARK &Box 14-1 Molecular Wire 213 142 Galvanic Cells 274 Demonstration 14-1 ‘The Human Salt Bridge 277 14-3. Standard Potentials 21 14-4. Nernst Equation 279 Box 14-2 £° and the Cell Voltage Do Not Depend on How You Write the Cell Reaction 280 Box 14-3 Latimer Find £° for a New Half-Reaction 282 14.5 E° and the Equilibrium Constant 283, Box 14-4 Concentrations in the Operating Cell 284 14-6 Cells as Chemical Probes 285 14-7 Biochemists Use E°” 288 15 Electrodes and Potentiometry 298 A Heparin Sensor 15-1 Reference Electrodes 299 15-2. Indicator Electrodes 301 Demonstration 15-1 Potentiometry with an Oscillating Reaction 302 15-3. What Is a Junction Potential? 303 15-4 How lon-Selective Electrodes Work 303 15-5 pH Measurement with a Glass Electrode 306 Box 15-1 Systematic Error in Rainwater pH Measurement: The Effect of Junction Potential 310 15-6 Ion-Selective Electrodes 31 15-7 Using Ion-Selective Electrodes 317 15-8 318 16 Redox Titrations 327 Chemical Analysis of High-Temperature Superconductors 16-1 The Shape of a Redox Titration Curve 328 Demonstration 16-1 Potentiometric Titration of Fe! with MnOy 332 16-2 Finding the End Point 332 16-3 Adjustment of Analyte Oxidation State 335 16-4 Oxidation with Potassium Permanganate 336 16-5 Oxidation with Ce? 337 Box 16-1 Environmental Carbon Analysis and Oxygen Demand 338 16-6 Oxidation with Potassium Dichromate 339 16-7 Methods Involving Iodine 340 Box 16-2 lodometric Analysis of High- ‘Temperature Superconductors 342 17 _Electroanalytical Techniques 348 How Sweet It Ist 17-1 Fundamentals of Electrolysi 349 Demonstration 17-1 Electrochemical Writing 350 Contents 17-2 Electrogravimetric Analysis 353 17-3 Coulometry 355 17-4 Amperometry 357 Box 17-1 Oxygen Sensors 358 Box 17-2 What Is an “Electronic Nose”? 360 17-5 Voltammetry 362 Box 17-3 The Electric Double Layer 365 17-6 Karl Fischer Titration of H,O 370 Demonstration 17-2 The Karl Fischer Jacks of a pH Meter a7 18 Fundamentals of Spectrophotometry 378 ‘The Ozone Hole 18-1 Properties of Light 379 18-2 Absorption of Light 380 Box 18-1 Why Is There a Logarithmic Relation Between Transmittance and Concentrat 382 18-3 Measuring Absorbance 383 Demonstration 18-1 Absorption Spectra 383 18-4 Beer's Law in Chemical Analysis 385 18-5. What Happens When a Molecule Absorbs Light? 387 Box 18-2 Fluorescence All Around Us 301 18-6 Luminescence 392, Box 18-3 Instability of the Earth's Climate 395, 19 Applications Of Spectrophotometry 402 Fluorescence Resonance Energy Transfer Biosensor 19-1 Analysis of a Mixture 402 19-2 Measuring an Equilibrium Constant: ‘The Scatchard Plot 407 19-3 The Method of Continuous Variation 408 CTtyRing-Down S pio Have anki dor a “ADR wih the Dealing with Noise21 Atomic Spectroscopy 453 ‘An Anthropology Puzzle 21-1 An Overview 454 Box 21-1 Mercury Analysis by Cold Vapor Atomic Fluorescence 456 21-2. Atomization: Flames, Furnaces, and Plasmas 456 21-3 How Temperature Affects Atomic ‘Spectroscopy 461 21-4 Instrumentation 462 21-5 Interference 466 21-6 Inductively Coupled Plasma— Mass Spectrometry 468 22 Mass Spectrometry 474 Droplet Electrospray 22-1 What Is Mass Spectrometry? 474 Box 22-1 Molecular Mass and Nominal Mass 476 Box 22-2 How Ions of Different Masses ‘Are Separated by a Magnetic Field 476 22-2 Oh, Mass Spectrum, Speak to M 428 Box 22-3 Isotope 482 22-3 Types of Mass Spectrometers 484 22-4 Chromstography—Mass Spectrometry 488 Box 22-4 Matrix-Assisted Laser Desorption/fonization 494 23 Introduction to Analytical Separations 501 Measuring Silicones Leaking from Breast Implants 23-1 Solvent Extraction 502 Demonstration 23-1 Extraction with Dithizone 504 Box 23-1 Crown Ethers 506 23-2. What Is Chromatography? 506 3-3 A Plumber's View of Chromatography 508 23-4. Efficiency of Separation sul Why Bands Spread 516 Box 23-2. Microscopic Description of Chromatography 522 24 Gas Chromatography 528 What Did They Eat in the Year 1000? 24-1. The Separation Process in Gas Chromatography 528 Box 24-1 Chiral Phases for Separating Optical Isomers 533 24-2 Sample Injection 538 24-3 Detectors Sal 24-4 Sample Preparation 547 24-5 Method Development in Gas Chromatography 549 25 High-Performance Liquid Chromatography 556 In Vivo Microdialysis for Measuring Drug Metabolism 25-1. The Chromatographic Process 557 Box 25-1 Monolithic Silica Columns 562 Box 25-2 “Green” Technology: Supercritical Fluid Chromatography 568 25-2 Injection and Detection in HPLC 570 25-3. Method Development for Reversed-Phase Separations 575 25-4 Gradient Separations 580 Box 25-3 Choosing Gradient Conditions and Sealing Gradients 582 26 Chromatographic Methods and Capillary Electrophoresis 588 Capillary Electrochromatography 26-1 Lon-Exchange Chromatography 589 26-2 Ton Chromatography 594 Box 26-1 Surfactants and Micelles 598 26-3 Molecular Exclusion Chromatography 599 26-4. Affinity Chromatography 602 Box 26-2, Molecular Imprinting 603 26-5. Principles of Capillary Electrophoresis 603 26-6 Conducting Capillary Electrophoresis, 610 26-7 Lab on a Chip 620 27 ~Gravimetric and Combustion Analysis 628 he Geologic Time Scale and Gravimetric Analysis, 27-1 An Example of Gravimetric Analysis 629 27-2. Precipitation 630 632 634 Btatistics of Sf fERSION solving Samples for Analysis ‘Contents. Gravimetric Determination of Iron as FeO, . Penny Statistics §. Statistical Evaluation of Acid-Base Indicators Preparing Standard Acid and Base . Using a pH Electrode for an Acid-Base Titration . Analysis of a Mixture of Carbonate and Bicarbonate . Analysis of an Acid-Base Titration Curve: ‘The Gran Plot 10. Kjeldahl Nitrogen Analysis, 11. EDTA Titration of Ca?* and Mg?* in Natural Waters 12. Synthesis and Analysis of Ammonium Decavanadate 13. Iodimetric Titration of Vitamin C 14. Preparation and Todometric Analysis of High-Temperature Superconductor 15. Potentiometric Halide Titration with Ag* 16. Flectrogravimetric Analysis of Copper 17. Polarographic Measurement of an Equilibrium Constant 18. Coulometric Titration of Cyclohexene with Bromine 19. Spectrophotometric Determination of Iron in Vitamin Tablets 20. Microscale Spectrophotometric Measurement of Iron in Foods by Standard Addition 21. Spectrophotometric Measurement of an Equilibrium Constant 22. Spectrophotometric Analysis of a Mixture: Caffeine and Benzoic Acid in a Soft Drink 23. Mn?" Standardization by EDTA Titration 24. Measuring Manganese in Steel by Spectrophotometry with Standard Addition 25. Measuring Manganese in Steel by Atomic Absorption Using a Calibration Curve 26. Properties of an Ion-Exchange Resin 27. Analysis of Sulfur in Coal by Ton Chromatography 28. Measuring Carbon Monoxide in Automobile Exhaust by Gas Chromatography 29. Amino Acid Analysis by Capillary Electrophoresis, 30. DNA Composition by High-Performance Liquid Chromatography 31. Analysis of Analgesic Tablets by High-Performance Liquid Chromatography 32. Anion Content of Drinking Water by Capillary Electrophoresis SPI Aa & Spreadsheet Topics 2-10. Introduction to Microsoft Excel 33 2-11 Graphing with Microsoft Excel 35 Problem 3-8 Controlling the appearance of a graph 51 4-1 Average, standard deviation, normal distribution 55 45° 1Test 64 47 Equation of a straight line 4-9. Spreadsheet for least squares 1 Problem 4-25 Adding error bars to a graph 16 5-2 Square of the correlation coefficient (R?) 83 Problem 5-14 Using TRENDLINE 93 6-8 Solving equations with Excel Goat. seex 11s 7-6 Precipitation titration curves 132 7-8 Multiple linear regression and experimental design 134 8-5 Using Goat. seex in equilibrium problems 153 Problem 8-27 Circular reference 156 9-5 Excel Goat seek and naming cells 176 11-9 Acid-base titration curves 218 12-4 EDTA titrations 237 Problem 12-18 Auxiliary complexing agents in EDTA titrations 247 Problem 12-20 Complex formation 248 13-1, Using Excel souver 253 13-2 Activity coefficients with the Davies equation 256 13-4 Fitting nonlinear curves by least squares 264 13-4 Using Excel soLveR for more than one unknown 265 19-1 Solving simultaneous equations with Excel SOLVER 405 19-1. Solving simultaneous equations by matrix inversion 406 Problem 24-29 Binomial distribution function for isotope patterns 555 Notes and References NRI Glossary GLI Appendixes API A. Logarithms and Exponents API B. Graphs of Straight Lines AP2 C. Propagation of Uncertainty AP3 D. Oxidation Numbers and Balancing Redox Equations APS E, Normality APS ‘APS APIL SCREGISTERED © i. anf StantaaW ER STON 4 ADDS NO Exercises MORERMARK & xiPreface One of our most pressing problems is the need for sources of energy to replace ol ‘The chart at the right shows that world production of oil per capita has probably ‘already peaked. Oil will play a decreasing role as an energy source and should be reve valuable as a raw material than as a fuel, There is also strong pressure t0 mini- nize the burning of fuels that produce carbon dioxide, which could be alterin Earth's climate, It is my hope that some of you reading this book will become scientists. engi- 1 enlightened policy makers who will find efficient, sustainable ways to har- ness energy from sunlight. wind, waves. biomass, and nuclear fission and fusion. Nuclear fission is far less polluting than burning oil, but difficult problems of waste ‘containment are unselved. Much coal remains, but coal creates carbon dioxide and pollution than any major energy source. There is a public misconception that hydrogen is a source of energy. Hydrogen requires energy to make and is only a means of storing energy. There are also serious questions about whether ethanol pro- vides more energy than is required for its production, More efficient use of energy will play a major role in reducing demand. No source of energy is sufficient if our population continues to grow. i e 2 Per copita production of of peaked inthe Goals of This Book 19708 ond is expected to decrease In coming ‘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 that will appeal to stud their primary interest is chemistry. [ intend the material to be lucid enough for nonchemistry majors yet to contain the depth required by ee Yaron ‘advanced undergraduates. This book grew out of an introductory 0% of area of mts whether oF not analytical chemistry course that I taught mainly for nonmajors at the eaeacaelb /A'\erocace ra Mab \ cease University of California at Davis and from a course for third-year forbiank \ | forsamse chemistry students at Franklin and Marshall College in Lancaster, Pennsylvania, What's New? In the seventh edition, quality assurance was moved from the back of the beok into Chapter 5 «0 emphasize the increasing importance attached to this subject and to link it closely to statistics and ealibration, Two chapters on activity coefficients and the syster ment of equilibrium from the sixth edition were condensed into Chapter 8. A pew, advanced treatment of equilibrium appears in Chapter 13. This chapter, which requires spreadsheets, is going to be skipped in intro- ductery courses but should be of value for advanced undergraduate or | Lit ‘graduate work, New topies in the rest of this book include the acidity of metal ions in Chapter 6, a revised disc ple of experimental design in Chapter 8. pH of zero charge for colloids atic te on of ion sizes and an e ‘Qualty essutance applice statics “Oi production data can be found at ttp/fopcomerldenen. Se also D. Goodstein, Out of Ges (ew Yorks W. W. Norton. 2004; KS. Delfeyes,Bevont Oil The View fram Hubbert's Peak (New Yor Farrar, Straus andl Giroux, 2005); and R.C. Duncan, “Wertd Breray Prades, Poplation Growth ae 0 eat tthe Olduval Gorge.” Paton and Ervironment 2M, 22, $03 tr HubberPeak.conDuncan ‘Oisi2000.40, Preface: xlFhocescence fesonarce ‘Analy ale energy arstor attached to . ~ eon tamrcane OE | vo voy oe on ge errs icrocogriton = lore such ‘8. ortbody exile . Subetate WB Rociart energy sbserber (concn) Pe Radiant energy emitter coop) Principle of operation of @ fucrescence resonance energy transfer biosensor in Chapter 10, monoclonal antibodies in Chapter 12, more on microelectrodes and the Karl Fischer titration in Chapter 17, self-absorption in fluorescence in Chapter 18, surface plas ‘mon resonance and intracellular oxygen sensing in Chapter 20, ion mobility spectrometry for airport explosive sniffers in Chapter 22. 8 microscopic description of chromatography in Chapter 23, illustrations of the effects of column parameters on separations in gas chro- ‘matography in Chapter 24, advances in liquid chromatography stationary phases and more ‘dotail on gradient separations in Chapter 25, automation of ion chromatography in Chapter 2 and sample concentration by sweeping in electrophoresis in Chapter 26, Updates to many existing topies are found throughout the book. Chapter 27 on gravimetric analysis now includes an example taken from the Ph.D. thesis of Marie Curie from 1908 and a description of how 20-year-old Arthur Holmes measured the geologic time seale in 1910, Applications AA basic tenet of this book is to introduce and illustrate topics with concrete. interes ‘xamples. In addition to their pedagogic vulue, Chapter Openers, Boxes, Demonstrations, find Color Plates are intended to help lighten the load of a very dense subject. ! hope you wll find these features interesting and informative. Chapter Openers show the relevance OF analytical chemistry t the real world and to other disciplines of science. ¥ can't come to Your classroom to present Chemical Den Bt igen tell you about some of my favorites and show you color photos of ho ane located near the center of the book. Boxes dis SO ERE/ dying or they New boxed applications i measure attograms of mass (Ch folecular wire (Chapter 14), Mee eae oo Se REGUS TERED.:\ VERSION ADDS NO pedagogic ool designed to teat have just read. There are Exerc QB ses a the Roo strupele ook. Problems PrefaceSpreadsh {s ure indispensable tools for science and engi : pea sd OC a you will never regret taking the time to lear to use them. The text 210 nS opal Intorcapt Cipains how to ume spreadsheets and ome problems ask you to F211 aw Sate ee apply them. If you are comfortable with spreadsheets, you will use = = ~ = = them even when the problem doesnot ak you fo. ATew of the [21 -#{ ¢[ [Seber foasae —foatete powerful built-in features of Microsoft Excel are described as they [S461 § __fr2 [o.sea2 [0.19612 are needed. These features include graphing in Chapter 2, statistical 5 functions and regression in Chapter 4, multiple regression for [Z| Highlight oolls EFS: _ experimental design in Chapter 7, solving equations with GoaL 8 | Type "= LINEST(B2:B5,A2:A5, TRUE, TRUE)" ‘SEEK in Chapters 6, 8, and 9, soLveR in Chapters 13 and 19, and 9 | Press CTRL + SHIFT + ENTER (on PC)| Ix operations in Chapter 18. 70 [Pres COMMAND RETURN on Nac) Spreadsheets ae Indispensable too. Other Features of This Book Terms to Understand Essential vocabulary, highlighted in boldface inthe text or, some times, in color in the margin, is collected at the end of the chapter. Other unfamiliar or new xt, but are not listed atthe end of the chapter. terms are italic in the Glossary All boldface vocabulary terms and many of the it slossary a the back of the book. ms are defined in the Appendixes Tables of solubility products, acid dissociation constants (updated to 2001 Jox potentials, and formation constants appear at the back of the book. You will also find discussions of logarithms and exponents, equations of a straight line, propagation of ceror, balancing tedox equations, normality, and analytical standards Notes and References ci values), jons in the chapters uppear at the end of the book Inside Cover Here are your trusty periodie table, physical constants, and other useful information, Supplements NEW! eBook This online version of Quantitative Chemical Analysis, Seventh Edition combines the text and all existing student media resources, along with additional eBook features. The eBook includes + Intuitive navigation to any section or subsection, as well as any printed book page number. + Tntext links to all glossary term definitions. * Bookmarking, Hi ind Notes fea allow students or instructors 10 add notes to any page. * A full glossary and index and full-text search, es, With all activity automatically saved, For instructors, the eBook offers unparalleled flexibility and customization options. includigg + Custom chapter sele« + Instructor notes: Instructors can incorporate notes used for their course into the ‘Students will automatically get the customized version, Notes can include text, Wi and even images. Students will access only chapters the instructor selects EERED | <9 Sy (> REGISTERED ON “VERSION Te Stent Web St, cn congestion fr experinggat may berepetced for your ue, Ahi We sit, you wil als id sts expe ; ADDS NO Jal of ChenealEdacatcn, afew dowsioadable Excel yprexdaety Gran pt hats 0 manly ln vale, Supplementary topics the Web se The Solutions Manual for Quantitative Chemical Analysis contains complete all problems. The Instructors’ Web Site, vv. whfreeman.conm/qea7e. has all illustrations and tables from the book in preformatted PowerPoint slides. Preface xvThe Peopie ‘A book of this size and complexity isthe work of many people. At W. H, Freeman and Com- pany, Jessica Fiorillo provided guidance and feedback and was especially helpful in ferreting, ‘out the opinions of instructors. Mary Louise Byrd shepherded the manuscript through pro- duction with her magic wand and is most responsible for creating the physical appearance of this book. Patty Zimmerman edited the copy with great care. The design was created by Diana Blume. Pages were laid out by Jerry Wilke and proofread by Karen Osborne, Photo editing and research was done by Cecilia Varas and Donna Ranieri, Pau! Rohloff had overall responsibility for production, Julian Roberts ofthe University of Redlands twisted my arm until I created the new Chap- ter 13, and he provided considerable content and critique. My consultants at Michelson Labora- tory, Mike Seltzer and Eric Erickson, were belpful, as always. Solutions to problems and exer- cises were checked by Samantha Havkins at Michelson Lab and Teh Yun Ling in Singapore. ‘My wife, Sally, worked on every aspect of this book and the Solutions Manual. She con- tributes mightily to whatever clarity and accuracy we have achieved. In Closing ‘Tis book is dedicated to the students who use it, who occasionally smile when they read it, ‘who gain new insight, and who fee! 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. I truly relish your comments, criticisms, suggestions, and corree- tions. Please address correspondence to me at the Chemistry Division (Mail Stop 6303), Research Department, Michelson Laboratory, China Lake, CA. 93555. Dan Harris Acknowledgments Tam indebted to users of the sixth edition who offered corrections and suggestions and to the many people who reviewed parts of the current manuscript. John Haberman at NASA pro- vided a great deal of help in creating the back cover of this book. Bill Schinzer (Piizet, Inc.) offered comments and information about the Karl Fischer titration. Athula Attygalle (Stevens Institute of Technology) pointed out my misinterpretation of Kielland’s “ion sizes.” which Jed 1o a revision of Chapter 8. Krishnan Rajeshwar University of ‘Texas, Arlington) had ‘many helpful suggestions, especially for electrochemistry. Carl E. Moore (Emeritus Profes- sor, Loyola University, Chicago) educated me on the history of the pH electrode and the pH ‘meter, Herb Hill (Washington State University) and G. A. Ficeman (New Mexico State Uni- versity) were most gracious in providing comments and information on ion mobility spec trometry. Nebojsa Avdalovie (Dionex Corporation) provided key information on automation of ion chromatography, Shigeru Terabe (University of Hyogo, Japan) and Robert Weinberger helped with electrophoresis. Other corrections, suggestions, and helpful comments were pro- vvided by James Gordon (Central Methodist University, EayettegMissouri), Dick Zare (Stan- ford University), D. Bax (Utrecht University, : vata (Macalester College), David Green (Albion College), J Instrument Company), David Riese (Purdudl stony Phase; ide AMON (University HEME Glen University Col Fepiumbia), People who reviewed parts dition 10 make suggestions for the ‘versity, Dean Atkinson (Portiargg@mte University RST few Mester Collegt- (University BMonte- Yor Genezo, Mark Bryan, vale), Daud Castillo (Worn), lng wey of Mor Bi aan CREE STILE verona Institue of Technolog). Angel / af Binghamton), John Ejnik (Ne Dale Hawley (Kansas State Univers Dan Heglund (South Dakota School ofWestern State University), Elizabeth Jensen (Aquinas College, Grand Rapids), Mark Krehling (University of Southern Indiana), Barbara Kramer (Truman State University), Brian Lamp (Truman State University), Lisa B. Lewis (Albion College), Sharon McCarthy (Chicago State University), David McCurdy (Truman State University), Mysore Mohan (Texas A&M University), Kenneth Mopper (Old Dominion University), Richard Peterson (Northern State University, Aberdeen, South Dakota), David Rahni (Pace University, Pleas- antvlle/Briarcliff), Gary Rayson (New Mexico State University), Steve Reid (University of Saskatchewan), Tracey Simmons-Willis (Texas Southem University), Julianne Smist (Springfield College, Massachusetts), Touradj Solouki (University of Maine), Thomas M. Spudich (Mereyhurst College), Craig Taylor Oakland University), Sheryl A. Tucker (Univer sity of Missouri, Columbia), Amy Witter (Dickinson College), and Kris Varazo (Francis Marion Univer VERSION ADDS NO vi0 The Analytical Process A BIOSENSOR FOR ARSENIC IN THE ENVIRONMENT’? 7 @ ‘sR protein bound bs a > Genes , ona Fe = Uses Operator ste comtas gene rcenite (binds to Bi eomressin seen oe operate ste) rs = ° xo rowalows gee Noles AR, kes Neots cresson eet Palade asic o © (6) Test sips exposed to citferent levels of crete, (Couneey JR va der Mex (©) How the genencally engineered DNA Werks. oe _ water from aquifers in contact wit arsenic-containing minerals. The analytical proble gi 3” et fsa al sry ey wt whch ane a tne 5 pr ri gS REGISTERED i), Pane! (a) shows 8 test strips impregnated with genetically engineered F. cogent? ‘whore genes are tured on by arsenite (HASO3”). When the strips are exposed (OMgmiing VERSION water, a blue spot develops whose size increases with the concentration of arsenili the ADDS NO water. By comparing the spot with a set of standards, we can estimate whether Qa is WATERMARK & above or below $0 ppb. We call the test strip a biosensor, because it uses biological of < Go ic this level causes vascular and skin diseases and cancer. nents in its operation, Panel (b) shows how the assay works. Genetically engineered DNA in ‘gene arsk, which encodes the regulatory protein ArsR, und the gene lacZ, which encod protein B-galactosidase. ArsR binds to regulatory sites on the gene t0 prevent DNA trans ton, Arsenite causes ArsR to dissociate from the gene and the cell proceeds to manufseture both AnsR and B-galactosidase. Then galactosidase transforms a synthetic, colorless substance called X-Gal in the test strip into a blue product. The more arsenite, the more intense the color. vint-drwChocolate is grect 10 cot, but not s0 easy 10 onaivee. [¥ H, reeman photo by K.Bendo} A diuretic makes you uncle A wasodlator aniorges blood vessels. Notes ondireferences ot sted ct he back of the book Chemical Abstracts the most comprehensive source for locating eices pubis in Chemisty journal, Sciinder i sofwore that ceccesses Chemicat Abstacts Bold terms should bo loorned. They are Isto ‘at ne end of the chopter and in the Glossary Gt the bock of he Book. Holezed words oe Jest importor, but many of thelr defiriions ‘are oko found in the Giessory Homogeneous: same throughout Volorogoneous difers from region to region Figure 0-1. Ceramic metiarond poste lect 10 grind sols into Fre powders. lo ‘C}y hocotate? has been the savior of many a student on the long night before a major assignment seas de. My’ fiveite chocolate bar, janined ith 33% fat and 47% supa, propels me ow mountains in California’ Sera Nevada In addition wo its high energy content chocolate packs faventa punch with the stimulant caffeine adits biccherical precursor, thecbromine. CHy | N N i a Bw San oF NNN \ CHy Thechromine Cettene [A diuretic, smooth muscle relaxant A central nervous sytem stimulant arive stimulant, and vasodilator ‘Too much caffeine is harmful for many people, and even stall amounts cannot be tolerated by some unlucky individuals. How much caffeine isin a chocolate bar? How does that amount ‘compare with the quantity in coffee or soft drinks? At Bates College in Maine, Professor Tom ‘Wenzel teaches his students chemical problem solving through questions such as these.* But, hew do you measure the caffeine content of a chocolate bar? ® EE 0-1 The Analytical Chemist's Job “Two students, Denby and Scott, began their quest at the library with a computer search for analytical methods. Searching with the key words “caffeine” and “chocolate.” they uncovered ‘numerous articles in chemistry journals. Reports titled “High Pressure Liquid Chromato- ‘praphic Determination of Theobromine and Caffeine in Cocoa and Chocolate Products”> described a procedure suitable forthe equipment in their laboratory.* Sampling The fi alysis is procuring a representative sample to measure—a process called sampling, Is all chocolate the same? Of course not. Denby and Scott bought ‘one chocolate bar in the neighborhood store and analyzed pieces of it. If you wanted to make broad statements about “caffeine in chocolate;” you would need to analyze a variety of chocolates from different manufacturers. You would also need to measure multiple samples of each type to determine the range of caffeine in each kind of chocolate ‘A pure chocolate bar is fairly homogeneous, which means that its composition is the same everywhere. It might be safe to assume that @ piece from one end has the same caffeine content as a piece from the other end, Chocolate with aymacadamia nut in the mille is an ‘example of a heterogeneous matcrial—one whoge conf@McitufMBitTagg from place to place. ‘The nut is different from the chocolate. To garny Iayou need 10 use a strategy different froan that used to sar now the average mass of chocolat ‘content of macadamia chocolate. VERSION ryeitert ADDF IN cca - WATERWARK Si oa Fine cia iy Imagine trying to grind chocolate! Denby and Scott froze the mortar and pestle with its lodPot Once the chocolate Sample Preparation ‘The first step in the procedure it by dissolving the fat in a hyd interfere with chromatography Lata ‘of chocolate with solvent, extract Mg to the inside of the chocolate. So, our and placed the pieces into mortar CHAPTER 0 The Analytical Process) Foe 0-2 cing tem cel ) recatennene so Sacto eae = cra re | es saeN| oo com cane oe ee stg ma sce a eine oarcecm ere raed ig age Sreieininnie ca pale es cinta ene siceegnts eae fing Scien cc re ance eaten ge it tea een ceuteig oe cae ars secre iene maar ees rinses eres ties sac een nnmem teense se eee er re tr aa este rasa ia heretic Sti pens enter ee emer yamae cane ~etheaeeemtenres some maimensmeniengtoecmcman tt Bee een re Sr cuca ee a cient ea ie nana aoe Re & analyte in water with the unknown solution containing 33.3 g of water ‘Before Denby and Scott could inject the unknown solution into a chromatog chemical analysis, they had to clean up the unknown even further (Figure 0-3). 7 chocolate residue in water contained tiny solid particles that would surely clog thas the tube. The cloudy, tan supernatant liquid (liquid above the packed solid) wa ina further attempt to remove tiny particles of solid from the liquid, It is critical to avoid injecting solids into a chromatography column, but th and centrifuged, it became a litle cleaner. But the liquid was never completely cleat enough time, more solid always seemed to precipitate from the filtered solution. Bole win your The tedious procedure described so far is called sample preparation—transforming sample into a state that is suitable for analysis. In this case, fat had to be removed from the 0-1 The Analytical Chemist's Job 3Figure 0-3 Contitugation ana tration cre Used fo separate undesired sod residve from tho oqueous zoktion of anciyies. CChromatograpty solvent is selected by © systematic tiakand-enor process described in ‘Chapter 25. the tunction of he acetic acid is {o reac! wilh negatively charged! exygen toms that lo on the slica surface and, when pot noutolzed,ghtly bind smal traction of Catfeine ond theobrorine ocetic act, siieoO ©, etieooH Binds onciyies Doge not bine very tatty enolyes sonaly Figure 0-4 Principle of aud chromatography. (0) Chromatography ‘opporohs with on utteiciet absorbance ‘monitor fo detect anaes ol the coluren ‘ute (b) Seporation ef cotteine and theobromine by chromatogtopty Cofteine is more solibe than thectomine in the hydrocarbon layer onthe patticies inthe column. Thertero, cate i retoined more strongly ond moves through the column more tlowty then theobromine. la thera supernatant Pee 5 =—— Rm # 0 45mierometer fee ermtuge || + supematant ea ontaring SocoWved arahies y ‘and ty pares Suspension! Insole Filer sotstion ~ Suspension cf sidinwaler chcolale containing dssched chocolate residue restie” saiyestrijocion | ir bosng water ito chomatogeapn chocolate, analytes had to be extracted into water, and residual solid had to be separated from the water. The Chemical Analysis (At Last!) Denby and Scot finally decided that the solution of in as they could make it in the time available. The next step was to inject solution into a chromatography column, which would separate the analytes and measure the quantity of each. The column in Figure 0-4a is packed with tiny particles of silica (SiO2) to which are attached long hydrocarbon molecules. Twenty microliters (20.0 X 10-*liters) of the chocolate extract were injected into the column and washed through with a solvent made by mixing 79 mL of pure water, 20 mi of methanol, and | mL of acetic acid. Caffeine is more soluble than theobromi the hydrocarbon on the silica surface, ‘Therefore. caffeine “sticks” to the coated silica part cles in the column more strongly than theobromine does. When both analytes arc flushed through the column by solvent, theubromine reaches the outlet before caffeine (Figure 0-4b). alytes was as ch Inject analy Salvent soliton » Soliton containing Hydrocarbon elects | both anaes . \ shomicaly bound 0 ue Scrvane care || / | Crromategrapy coh packed ‘SiO patices| oom compuer @ CHAPTER 0 The Analytical Process