Daniel C harris quantitative chemical analysis, 8th edition 2010

“The Experiment” by Sempé © C Charillon, Paris QUANTITATIVE CHEMICAL ANALYSIS Publisher: Clancy Marshall Senior Acquisitions Editor: Jessica Fiorillo Marketing Manager: John Britch Media Editor: Dave Quinn Editorial Assistant: Kristina Treadway Photo Editor: Ted Szczepanski Cover and Text Designer: Vicki Tomaselli Senior Project Editor: Mary Louise Byrd Illustrations: Network Graphics, Precision Graphics Illustration Coordinators: Bill Page, Eleanor Jaekel Production Coordinator: Julia DeRosa Composition and Text Layout: Aptara, Inc Printing and Binding: RR Donnelley Library of Congress Control Number: 2009943186 ISBN-13: 978-1-4292-1815-3 ISBN-10: 1-4292-1815-0 © 2010, 2007, 2003, 1999 by W H Freeman and Company All rights reserved Printed in the United States of America First Printing W H Freeman and Company 41 Madison Avenue New York, NY 10010 Houndmills, Basingstoke RG21 6XS, England www.whfreeman.com QUANTITATIVE CHEMICAL ANALYSIS Eighth Edition Daniel C Harris Michelson Laboratory China Lake, California W H Freeman and Company New York This page intentionally left blank BRIEF CONTENTS The Analytical Process 1 Chemical Measurements 13 Tools of the Trade 29 Experimental Error 51 Statistics 68 Quality Assurance and Calibration Methods Chemical Equilibrium 96 117 Activity and the Systematic Treatment of Equilibrium 142 Monoprotic Acid-Base Equilibria 162 Polyprotic Acid-Base Equilibria 185 10 Acid-Base Titrations 205 11 EDTA Titrations 236 12 Advanced Topics in Equilibrium 258 13 Fundamentals of Electrochemistry 279 18 Applications of Spectrophotometry 419 19 Spectrophotometers 445 20 Atomic Spectroscopy 479 21 Mass Spectrometry 502 22 Introduction to Analytical Separations 537 23 Gas Chromatography 565 24 High-Performance Liquid Chromatography 595 25 Chromatographic Methods and Capillary Electrophoresis 634 26 Gravimetric Analysis, Precipitation Titrations, and Combustion Analysis 673 27 Sample Preparation 699 Notes and References NR1 14 Electrodes and Potentiometry 308 Glossary GL1 15 Redox Titrations 340 Appendixes AP1 16 Electroanalytical Techniques 361 Solutions to Exercises S1 17 Fundamentals of Spectrophotometry Answers to Problems AN1 393 Index I1 v This page intentionally left blank CONTENTS Preface The Analytical Process 3-5 Propagation of Uncertainty from Systematic Error The “Most Important” Environmental Data Set of the Twentieth Century 0-1 Charles David Keeling and the Measurement of Atmospheric CO2 0-2 The Analytical Chemist’s Job 0-3 General Steps in a Chemical Analysis 11 Box 0-1 Constructing a Representative Sample 12 Box 3-2 Keeling’s Exquisitely Precise Measurement of CO2 xiii Chemical Measurements Biochemical Measurements with a Nanoelectrode 1-1 1-2 1-3 1-4 SI Units Chemical Concentrations Preparing Solutions Stoichiometry Calculations for Gravimetric Analysis 1-5 Introduction to Titrations Statistics Is My Red Blood Cell Count High Today? 4-1 Gaussian Distribution 4-2 Confidence Intervals 4-3 Comparison of Means with Student’s t 60 62 68 68 68 73 76 Box 4-1 Choosing the Null Hypothesis in Epidemiology 79 13 16 19 4-4 Comparison of Standard Deviations with the F Test 4-5 t Tests with a Spreadsheet 4-6 Grubbs Test for an Outlier 4-7 The Method of Least Squares 4-8 Calibration Curves 80 82 83 83 87 21 22 4-9 A Spreadsheet for Least Squares 13 13 Box 4-2 Using a Nonlinear Calibration Curve 88 89 Box 1-1 Reagent Chemicals and Primary Standards 23 1-6 Titration Calculations Tools of the Trade Quartz Crystal Microbalance in Medical Diagnosis 2-1 Safe, Ethical Handling of Chemicals and Waste 2-2 The Lab Notebook 2-3 Analytical Balance 2-4 Burets 2-5 Volumetric Flasks 2-6 Pipets and Syringes 2-7 Filtration 2-8 Drying 2-9 Calibration of Volumetric Glassware 2-10 Introduction to Microsoft Excel® 2-11 Graphing with Microsoft Excel Reference Procedure Calibrating a 50-mL Buret Experimental Error Experimental Error 3-1 Significant Figures 3-2 Significant Figures in Arithmetic 3-3 Types of Error Box 3-1 Case Study in Ethics: Systematic Error in Ozone Measurement 3-4 Propagation of Uncertainty from Random Error 24 29 Quality Assurance and Calibration Methods The Need for Quality Assurance 97 Box 5-1 Control Charts 99 5-2 Method Validation 49 51 51 51 52 55 55 57 96 5-1 Basics of Quality Assurance 29 30 31 31 35 37 38 40 41 42 43 46 96 Box 5-2 The Horwitz Trumpet: Variation in Interlaboratory Precision 5-3 Standard Addition 5-4 Internal Standards 5-5 Efficiency in Experimental Design Chemical Equilibrium Chemical Equilibrium in the Environment 6-1 The Equilibrium Constant 6-2 Equilibrium and Thermodynamics 6-3 Solubility Product Box 6-1 Solubility Is Governed by More Than the Solubility Product Demonstration 6-1 Common Ion Effect 6-4 Complex Formation Box 6-2 Notation for Formation Constants 6-5 Protic Acids and Bases 6-6 pH 6-7 Strengths of Acids and Bases Demonstration 6-2 The HCl Fountain Box 6-3 The Strange Behavior of Hydrofluoric Acid Box 6-4 Carbonic Acid 100 103 106 109 110 117 117 118 119 121 122 122 124 124 126 128 130 131 132 134 vii Activity and the Systematic Treatment of Equilibrium Hydrated Ions 7-1 The Effect of Ionic Strength on Solubility of Salts Demonstration 7-1 Effect of Ionic Strength on Ion Dissociation Box 7-1 Salts with Ions of Charge Ն| 2| Do Not Fully Dissociate 7-2 Activity Coefficients 7-3 pH Revisited 7-4 Systematic Treatment of Equilibrium Box 7-2 Calcium Carbonate Mass Balance in Rivers 7-5 Applying the Systematic Treatment of Equilibrium 219 10-6 Finding the End Point with Indicators 220 Box 10-2 What Does a Negative pH Mean? Demonstration 10-1 Indicators and the Acidity 221 of CO2 142 142 143 Box 10-3 Kjeldahl Nitrogen Analysis Behind the Headlines 143 145 145 149 150 153 223 223 10-7 Practical Notes 10-8 Kjeldahl Nitrogen Analysis 224 225 10-9 The Leveling Effect 10-10 Calculating Titration Curves with Spreadsheets Reference Procedure Preparing Standard Acid and Base 226 235 11 EDTA Titrations 236 236 Ion Channels in Cell Membranes 153 237 11-1 Metal-Chelate Complexes Monoprotic Acid-Base Equilibria Measuring pH Inside Cellular Compartments 8-1 Strong Acids and Bases Box 8-1 Concentrated HNO3 Is Only Slightly Dissociated 8-2 Weak Acids and Bases 8-3 Weak-Acid Equilibria Demonstration 8-1 Conductivity of Weak Electrolytes Box 8-2 Dyeing Fabrics and the Fraction of Dissociation 8-4 Weak-Base Equilibria 8-5 Buffers Box 8-3 Strong Plus Weak Reacts Completely Demonstration 8-2 How Buffers Work viii 163 11-2 11-3 11-4 11-5 238 EDTA EDTA Titration Curves Do It with a Spreadsheet Auxiliary Complexing Agents 240 243 245 246 Box 11-2 Metal Ion Hydrolysis Decreases the Effective Formation Constant for EDTA Complexes 163 165 166 11-6 Metal Ion Indicators Demonstration 11-1 Metal Ion Indicator Color Changes 167 169 11-7 EDTA Titration Techniques Box 11-3 Water Hardness 170 171 174 176 185 Proteins Are Polyprotic Acids and Bases 185 186 Box 9-1 Carbon Dioxide in the Air and Ocean Box 9-2 Successive Approximations 189 191 Diprotic Buffers Polyprotic Acids and Bases Which Is the Principal Species? Fractional Composition Equations Isoelectric and Isoionic pH 193 194 195 197 199 Box 9-3 Isoelectric Focusing 200 10 Acid-Base Titrations 10-1 10-2 10-3 10-4 10-5 162 Polyprotic Acid-Base Equilibria 9-1 Diprotic Acids and Bases 9-2 9-3 9-4 9-5 9-6 162 Box 11-1 Chelation Therapy and Thalassemia 12 Advanced Topics in Equilibrium 12-1 12-2 12-3 12-4 Acid-Base Titration of a Protein 205 Titration of Strong Base with Strong Acid Titration of Weak Acid with Strong Base Titration of Weak Base with Strong Acid Titrations in Diprotic Systems Finding the End Point with a pH Electrode 206 208 210 212 215 Box 10-1 Alkalinity and Acidity 216 249 251 253 258 Acid Rain 258 General Approach to Acid-Base Systems Activity Coefficients Dependence of Solubility on pH Analyzing Acid-Base Titrations with Difference Plots 259 262 265 270 13 Fundamentals of Electrochemistry 279 Lithium-Ion Battery 13-1 Basic Concepts Box 13-1 Ohm’s Law, Conductance, and Molecular Wire 13-2 Galvanic Cells 205 247 249 Demonstration 13-1 The Human Salt Bridge 13-3 Standard Potentials 13-4 Nernst Equation Box 13-2 E° and the Cell Voltage Do Not Depend on How You Write the Cell Reaction Box 13-3 Latimer Diagrams: How to Find E° for a New Half-Reaction 279 280 283 284 286 287 288 290 292 Contents Methane: chemical ionization, 505 chromatography, 545 greenhouse gas, 449b isotopic composition, 509b protonated, 505, 505i ring-down spectroscopy, 445b separation, 571 Methanesulfonate, hydration number, 142t Methanesulfonic acid, 142t, 669p Methanol: critical constants, 606t density, 25p diffusion coefficient, 551t eluent strength, 604t, 621i HPLC solvent, 618 pKa, 234p solvent-bonded phase interface, 604b ultraviolet cutoff, 604t Methionine, 187t Method blank, 98 Method detection limit, 105 Method development: electrophoresis, 664–665 gas chromatography, 587–589 HPLC, 617–628 Method of continuous variation, 425–427 Method validation, 100 Methoxide, 128 Methyl acetamide hydration number, 142t Methylamine, 127, 142t, 237 Methylammonium chloride, 133 Methylammonium ion, 127 Methylarsonate, 114p Methyl borate, 708, 708t N,NЈ-Methylenebisacrylamide, 648i Methylene blue, 298t, 346t N-Methylformamide, 663 Methyl isobutyl ketone, 225i Methyl oleate, 557t Methyl orange, 221t 3-Methyl-2-pentanone, 532p 4-Methyl-2-pentanone, 511i, 512 Methylphenidate, 633p Methyl red, 221t, 249d, 423i, 424 Methyl stearate, 557t Methyl t-butyl ether, 592p, 604t Methyl thymol blue, 251i, 440p Methyl violet, 221t Metric ton, 15t Micellar electrokinetic chromatography, 101i, 662–664 Micelle, 442p, 444p, 540d, 645b, 662 Michelson, A., 468m Michelson-Morley experiment, 468m Micro, 15t Microarray, 413 Microbalance: GaPO4, NR1 (2.2) quartz, NR1 (2.4) vibrating cantilever, NR1 (2.3) Micro cell, 399i Microdialysis probe, 666 Microelectrode, 383–384 Microelectrode array, 384 Microequilibrium constant, 255p Microfluidic device, 665–667 Microliter pipet, 39i Microphone, 460b Micropipet, 38–39 failure statistics, 49p Microporous particle, 599 Microreactor, 665 I16 Microscale titration, 37 Microscopic description of chromatography, 558b Microwave: bomb, 223 digestion, 412, 707, 709 extraction, 710–711, 711i oven, 41 radiation, 395i spectroscopy, 186i Migration, 374 Migration time, 654, 664 Mile, 16m, 26p Milk, 130i, 224b, 527b Milk of magnesia pH, 130i Milli, 15t Milliliter, 15t Millimeter Hg, 15t Millisecond, 13b Mine, acid drainage, 117b, 130i Mineral age, 673b Mineral oil, 399 Minimum detectable concentration, 103, 104 MINVERSE, 423 Mirror image spectra, 408i, 410i Miscibility, 538m Mitochondrion, 303p, 413, 651 Mixed-mode ion-exchangers, 714 Mixed operations, uncertainty, 58 Mixing chamber, 577 Mixing coil, 427i, 428, 429m Mixture: analysis, 419–423 titration, 689–690 mL (milliliter), 15t MMULT, 423 Mobile phase, 542 Mobility, 314, 518, 651, 652–656 MOBS, 179t Modulation, 491 Mohr pipet, 39i Moisture removal, 41t mol, 13, 14t, 16 Molality, 17 Molality-molarity conversion, 129t Molar absorptivity, 396 Molarity, 16 Molarity-molality conversion, 129t Mole, 13, 14t, 16, 21m Mole balance, 691 Molecular conductance, 283b Molecular exclusion chromatography, 543, 544i, 609i, 647–649 desalting, 647 gels, 647, 648i Kav, 647 molecular mass determination, 648 void volume, 647 Molecular ion, 504, 505m, 507, 511 Molecular light switch, 433 Molecularly imprinted polymer, 650b, 713 Molecular mass calibration standard, 649i definitions, 16, 504b determination, 648, 664 electrospray of proteins, 526–528 uncertainty, 63 Molecular orbital, 404 Molecular sieve, 571, 577i Molecular vibration, 405 Molecular wire, 283b Molybdenum, permanganate titration, 349t Monochromatic light, 396, 396m, 398 Monochromator: artifacts, 411b bandwidth, 452–453 dispersion, 452 emission, 410i excitation, 410i filter, 454, 455i grating, 411b, 446i, 447i, 450–453 resolution, 452 spectrophotometer, 396 slit, 446i, 447i Monoclonal antibody, 649i, 650 Monodentate ligand, 237 Monohydrogen oxalate, 133 Monohydrogen phosphate, 134 Monohydrogen phthalate, 192 Monolayer, 363, 369, 604b Monolithic column, 601b, 634 Monoprotic acids and bases, 162–181 fractional composition, 197–198 titrations, 208–212, 226–229 MOPS, 179t MOPSO, 179t, 320t Morphine, 204p, 632p 4-(N-Morpholino)butanesulfonic acid, 179t 2-(N-Morpholino)ethanesulfonic acid, 178t, 208, 227m 3-(N-Morpholino)-2hydroxypropanesulfonic acid, 179t, 320t 3-(N-Morpholino)propanesulfonic acid, 179t Mortar, 6i, 705 Mother liquor, 40, 679 MSn, 526 MTBE, 139p Mull, 399 Mullite mortar, 705 Multidentate ligand, 237 Multielement detection, 490–491 Multiple flow paths, 556 Multiple linear regression, 110–111 Multiplication: significant figures, 53 uncertainty, 58, 62t Multiplication stage (CCD), 458i, 459 Murexide, 250t, 251i Muscle, 185b Mussel, 495i Mylar beam splitter, 471 Myoglobin, 185b, 602i Myosin, 664i, 671p Myricetin, 622 n (nano), 15t N (newton), 14, 14t v (frequency), 394 NADH, 298t NADPH, 298t Nafion, 41t, 384, 389p, 509b Nano, 15t Nanoelectrode, 13b Nanometer, 395i Nanaoparticle, 29b, 381i, 383i, 391p, 417p, 550i, 649i Nanotube, 650i Naphtholphthalein, 221t Naproxen, 602, 603i, 713 Naringenin, 622 Narrow-bore column, 588t National Fire Protection Association label, 30, 30i National Institute of Standards & Technology, 56, 102, NR2 (3.1) pH reference buffers, 320t National measurement institutes, 96 Natural gas, 435b, 582i Natural logarithm, 61 Natural water: ions, 643i metal ions, 268–269 Nebulization, 482, 483i Nebulizer, 519, 520i Negative chemical ionization, 506 Negative pH, 220b Neocuproine, 402 Neon isotopes, 502m Nephelometry, Glossary Nernst, W., 287m Nernst equation, 288–291, 293 glass electrode, 318 ion-selective electrode, 324, 325, 327 Nerve cell, 13b, 236b Nessler’s reagent, 715t Neurotensin, 602i Neurotransmitter, 384 Neutral pH, 130 Neutral red, 221t Neutron mass, 508t Newton, 14, 14t Newton’s law, 26p Nickel: crucible, 708t EDTA titration, 252 gravimetric analysis, 675t, 681 masking, 253 ore, 702 San Francisco Bay, 236 Nickel-63, 518, 581 Nickel-metal hydride battery, 279b, 305p Nickel vessel, 685 Nicolsky-Eisenman equation, NR8 (14.25) Nicotinamide adenine dinucleotides, 298t Nicotine, 213i, 215, 592p, 632p “Nines” (purity nomenclature), App K Ninety-six-well plate, 714, 715i NIST traceable standard, App K Nitramine, 221t Nitrate: coprecipitation, 679m depolarizer, 368 dichromate titration, 351 field effect transistor, 334 gravimetric analysis, 675t ion-selective electrode, 328b, NR9 (14.31) lake sediment, 699, 700i mass spectrometry, 592p reduction, 349 Nitric acid: digestion, 707, 710 fuming, 709 Ka, 163b oxidant, 341t role in gravimetric analysis, 679 strength, 130t, 220b Nitric oxide, 77, 258b, 352b, 413, 505, 592p Nitrides, 707 Nitriles, 615 Nitrilotriacetic acid, 239, 239i, 403m Nitrite, 95p, 349, 356t, 358p, 416p, 477p, 592p, NR23 (27.30) p-Nitroaniline, 220b p-Nitroanilinium ion, 220b 4-Nitrobenzamide, 226m 2-Nitrobenzoic acid, 308b Nitrogen: air, 76–77 analysis, 683–685 Index atomic emission, 488, 490 bound, 352b chemiluminescence detector, 582, 587 combustion analysis, 683–685 detector, 581, 612t diffusion coefficient, 551t Dumas method, 224b elemental analysis, 683–685 gas chromatography, 574–576 isotope abundance, 508t Kjeldahl analysis, 223–225, 709 liquid, 2, 340b purification, NR11 (16.25) separation, 571 thermal conductivity, 580t Nitrogen oxide air, 349 electrode, 330 reduction, 710 Nitrogen-phosphorus detector, 580t, 581, 587, 589t Nitrogen rule, 507 Nitromethane hydration number, 142t Nitron, 675t, 676t, 694p p-Nitrophenol, 221t 2-Nitrophenyl octyl ether, 327 1-Nitropropane, 573t 2-Nitropropane, 382i 1-Nitroso-2-naphthol, 675t, 676t Nitrous acid, permanganate titration, 349t Nitrous oxide (N2O), 60b, 77, 352b, 449b, 483t, 700i dynamic reaction cell, 497–498 Nobel Prize, 76, 236b, 377i, 411b, 431m, 458m, 468m, 502m, 515m, 519m, 543m, 651, 674, 674m, NR11 (17.1) Nobias Chelate-PA1, 640i Noble gas, 27p Noise, 105, 458i, 459, 472–474, 492i root-mean-square, NR15 (20.19) Nominal mass, 504b Nomograph, eluent strength, 621i Nonaqueous titration, 225–226, NR6 (10.27) Nonbonding electrons, 504, 504i Nonbonding orbital, 404, 405i Nondispersive spectrometer, 460b Nonlinear calibration curve, 88b, 88i Nonlinear least-squares curve fitting, NR2 (4.6) Nonlinear regression, 272–274 Nonpolar, 236b Nonpolarizable electrode, 366 Nonresonant ion, 513 Nonsuppressed ion chromatography, 645 Nonwetting agent, 707 Norepinephrine, 613, 669p Normal alkane, 19 Normal distribution, 68m Normal error curve, 70i, 71 Normality, App E Normalization, 71 Normalized peak area, 654 Normal-phase chromatography, 603, 609i NORMDIST, 71–72 Nose, electronic, 372b Notch filter, 454 Notebook, 31, 700 NOx reduction, 710 NTA (nitrolotriacetic acid), 239, 239i, 403m N-terminal residue, 185b n-Type semiconductor, 332 Index Nuclear binding energy, 535p Nuclear energy, 435b Nuclear fuel reprocessing, 714 Nucleation, 676 Nucleic acid sequencing, 502 Nucleotide base pairing, 442p Nujol, 399 Null hypothesis, 76, 79b Null position sensor, 33 Number, spaces in, 13m Nutrition label, 105i ⍀ (ohm), 14t Oasis® sorbents, 714i Oberlin College, 362m Occlusion, 679 Ocean: acidification, 5, 189b CO2 sensor, 440p pH, 117b sodium chloride, 17 trace metal analysis, 497b trace metals, 640 Octadecyl bonded phase, 600, 604b, 621t Octanoic acid, 631p Octanol, 206m Octopole ion guide, 525i Octyl bonded phase, 600, 621t ODS (octadecylsilane), 600 Oestrogen, 79b Official Methods of Analysis, NR1 (0.6) Ohio State University, 712 Ohm (⍀), 14t, 282 Ohm’s law, 282 plot (electrophoresis), 657 Ohmic drop, 383–384 Ohmic potential, 364 Oil, 385 Oleic acid, 105i Oleum, 220b On-column injection, 578i, 579, 589 One-tailed test, 79, 80i, 82 Open-air sampling (mass spectrometry), 529–531 Open-circuit voltage, 364m Open tubular column, 543, 547, 557, 566–572, 577i, 587–589 van Deemter equation, 555m Opium, 665 Opsin, 456b Optical density, 396 Optical fiber, see Fiber optic Optical isomer separation, 602, 603i, 606b Optical train, 446i, 447i Optic nerve, 456b Optimization, 110, NR3 (5.13) Optode, 462 Optrode, 462 Orange peel, 583 Orbital, 404 Orbitrap, 510, 516–517, 518i, 529 Order of magnitude, 13 Ordinate, 15 Ore, 702, 707 Organic carbon, 352b Organic material, dissolution, 708–710 Organic peroxide, dichromate titration, 351 Organic structures, 136 Organohalide determination, 697p Oscillating reaction, 313d, NR8 (14.6), NR8 (14.7), NR8 (14.9) Osmium, 374, 375i Osmium tetroxide, 706 Osmolality blood test, 323t Outer cone, 483i Outlier, 83, 103b Ovalbumin, 200b, 602i, 664i, 671p Overall formation constant, 124b, 246 Overhead projector, 398d Overloading (chromatography), 557, 559i, 610 Overpotential, 364, 365t, 367, 377 Oversulfated chondroitin sulfate, 651, 651i Oxalate: barium oxalate solubility, 269–270 homogeneous precipitant, 678t permanganate standardization, 350 precipitation titration, 693t transferring binding, 417p Oxalic acid: acid dissociation, 133–134 buffer, 193–194 permanganate titration, 22, 24, 349t principal species, 196 Oxaloacetate, 298t Oxidant, 280 Oxidation, 280 catalyst, 684m catalytic, 352b number, App D organic material, 708–710 photochemical, 352b TiO2 catalyst, 352b total organic carbon, 352b Oxidation catalyst, 684m Oxidation state, 292b Oxidizability, 352b Oxidizing acid, 707 Oxidizing agent, 280, 706t Oxidizing strength, 288t Oxine, 359p, 540m, 676t Oxoprenolol, 663i Oxygen: blood test, 323t cell consumption, 436 COD, 391p cyclic voltammetry, 382i demand, 352b diffusion coefficient, 551t effect on gas chromatography column, 571, 576 electrode, 371b elemental analysis, 684 formal potential, 298t indicator beads, 436, 437i iodometric titration, 356t isotope abundance, 508t myoglobin binding, 185b optode, 462 overpotential, 365t oxidant, 341t polarogram, 378i polarographic waves, 378 pyrolysis analysis, 684 removal, 76, 378, 577i, NR11 (16.25) sensor, 371b, 433i, 436–437 separation, 571 thermal conductivity, 580t ultraviolet absorption in chromatography, 610 Oxygen trap in gas chromatography, 576 Ozone: absorption cross section, 416p absorption spectrum, 393b allowed level, 55b atmospheric, 14, 15i, 393b, 394 bound nitrogen analysis, 352b Dobson unit, 416p greenhouse gas, 449b iodometric titration, 356t measurement, 55b monitor, 55b nitrogen chemiluminescence detector, 582 oxidant, 341t perchlorate formation, 328b sulfur chemiluminescence detector, 582 Ozone hole, 14, 15i, 393b, 394 p (pico), 15t P (peta), 15t Pa (pascal), 14, 14t PAB ion exchanger, 637t Packaging to prevent evaporation, 492 Packed column, 543, 557, 571–572 van Deemter equation, 555m Paired t-test, 78–79 Paleothermometry, 595b Pales, J., Palladium, masking, 253 Palladium nitrate, 485 Paper mill, 117b Paprika, 543i Parallax, 36 Parr oxidation, 709 Particle: growth (precipitate), 676 sampling, 701–705 size (in chromatography), 572, 596–598, 596i, 597i, 598t standard sieve size, 702t Partition chromatography, 543, 544i Partition coefficient, 538, 546, 557 Partition ratio, 545m Parts per billion, 19 Parts per million, 19 Pascal, 14, 14t Passivation, App K Patent, 31m Pathlength, optical, 661i Patton & Reeder’s dye, 251i Paul, W., 515m Pauling, L., 674m PDB, 509b Peak: area measurement, 580 broadening (chromatography), 558b current, 382, 382i doubling (HPLC), 610 shape (electrophoresis), 659–661 Pee Dee belemnite (PDB), 509b PEEK, 616 Penetration depth, 464 Penicillin G, 650b Pentafluorobenzyl bromide, 592p Pentagonal bipyramidal coordination, 239i Pentaiodide, 351m Pentane: density, 48p eluent strength, 604t ultraviolet cutoff, 604t 2-Pentanone, 573t Pen thickness, 561p Pentobarbital, 505i Peptide bond, 185b cleavage, 528–529 Peptide nucleic acid (PNA), 465 Peptization, 679 Percent composition, 17 Percent relative uncertainty, 57 Percent transmittance, 396 I17 Perchlorate: biosensor, 372 gravimetric analysis, 675t groundwater, 106i ion-selective electrode, 329t Mars, 308b, 328b protein solubility, 650 urine, 113p Perchloric acid: density, 27p digestion, 706t, 710 hydrate, 127 oxidant, 341t precautions, 710 strength, 130t, 220b, 225i titrant in acetic acid, 225–226 use, NR22 (27.17) Perfluorokerosene, 510 Perflurotributylamine, 510 Performance qualification sample, 617 Performance test sample, 99 Perfusion blood test, 323t Periodate, 341t, 356t Peristaltic pump, 427i, 709 Permanent hardness, 253b Permanganate: dichromate titration, 351 extraction, 542b iodometric titration, 356t oxalate titration, 22, 24 oxidant, 341t, 349–350 oxidizability, 352b spectrum, 439p titration, 345d Peroxide: catalytic decomposition, 412 dichromate titration, 351 electrochemical detection, 615 flux, 707, 708t preoxidation, 348 Peroxyborate, 358p Peroxydisulfate, 223, 341t, 348, 349t, 352b, 356t cleaning solution, 36, NR1 (2.15) Persian coin, 18 Persistence of end point, 386 Persulfate, 348 Pesticide, 334, 432, 570b, 583, 710–711, 714 Pestle, 6i, 705 Peta, 15t PETN, 519i Petroleum, 509b Pewter, 479b p Function, 685 pH: activity, 149 common substances, 130i critical care profile, 323t definition, 129, 149 electrode, 317–323, 328 fish survival, 130i fluorescent beads, 162b from cell voltage, 295–296 Hϩ activity coefficient, 148i intermediate form of diprotic acid, 190, 191b, 192 intracellular, 162b introduction of term, 129m ion-selective electrode, 328, 339p iridium electrode, 323, NR8 (14.20) measurement, 319, NR8 (14.13) measurement errors, 319–321, 322b negative, 220b ocean, 117b, 189b, 202p phosphorylation, 303p pOH, 164 I18 principal species, 195–197 scale, 130 spectrophotometric measurement, NR12 (18.4) standards, NR8 (14.13) uncertainty, 62 zero charge, 201 Phagocytosis, 162b Pharmaceutical: illegal drug use, 699b ion exchanger application, 641 optical isomer analysis, 547, 602, 606b plasma extraction, 712 purity analysis, 101i sewage analysis, 524–525 tablet analysis, 614, 614i Phase boundary, 286 Phase diagram, 606b Phase transfer catalyst, 542b Phase transfer of permanganate, 542b pH effects: affinity chromatography, 649 capillary electrophoresis, 654, 658, 658i EDTA complex formation, 242–243 enzyme reaction rate, 172i extractions, 539–540 formal potential, 297–301 silica, 599–600, 601 1,10-Phenanthroline, 304p, 540 Phenobarbital, 672p Phenol, 133m, 144, 604b, 615 Phenolate, 133m, 144 Phenolphthalein, 219m, 221t, 398d Phenol red, 221t Phenosafranine, 346t Phenylalanine, 187t, 553i Phenyl bonded phase, 621t Phenylhydrazine, 182p Phenyl lithium, 234p Phenylmethylpolysiloxane, 586 Phenyl stationary phase, 600 Pheochromcytoma, 384 pH measurement, NR8 (14.13) pH meter: as potentiometer, 286d Beckman, 318m calibration, 319 history, NR8 (14.12) resistance, 293b terminals, 287 use, 319 US Standard connector, 287m Phoenix Mars Lander, 308b, 323, 328, 328b, 339p pH of zero charge, 201 Phosphate: buffer, 618t coprecipitation in coral, 679i gravimetric analysis, 675t homogeneous precipitant, 678t permanganate titration, 349t precipitation titration, 693t protonated forms, 133–134 reference buffers, 321t salting out, 650 Phosphide, 706 Phosphine, 289 Phosphor, 407b Phosphorescence, 406–407 Phosphoric acid, 134, 178t, 179t, 706t Phosphorus: atomic emission, 488, 490 detector, 581 flame photometric detector, 587 isotope abundance, 508t phosphomolybdate analysis, 695p Phosphorous acid, 354t Phosphorus pentoxide, 41t, 683 Phosphorylase, 200b, 664i, 671p Photoaction spectrum, 435b Photocell, 434b Photochemical oxidation, 352b Photoconductive detector, 459 Photodiode array, 457, 459t, 612, 613i Photoelectron spectroscopy, 504i Photoionization detector, 580t, 582, 587 Photomultiplier, 446i, 447, 447i, 455–456, 459t Photon, energy, 394, 395–396 Photooxidation, 352b, 391p Photosynthesis, 435b Phototube, 454 Photovoltaic detector, 459 Photovoltaic power, 434b pH-sensitive field effect transistor, 334 Phthalate, 192, 320t, 645m, 662 o-Phthaldialdehyde, 429, 666m Phthalic acid, 192 Physical gel, 664 Phytoplankton, 189b, 536p Phytoremediation, 252m Pi bonding electrons, 504, 504i Pickling, App K Pico, 15t Picoampere, 13b Picolinic acid, 203p Picric acid, 439p Piezo alerting buzzer, 167d Piezoelectric crystal, 29b, 487 Pigment separation, 542m, 543i Pike, M., 79b Pion exchanger, 637t Pi orbital, 404 Piperazine, 166, 680 Piperazine-N,NЈ-bis(4-butanesulfonic acid), 178t Piperazine-N,NЈ-bis(2-ethanesulfonic acid), 178t, 179t Piperazine-N,NЈ-bis(3-propanesulfonic acid), 178t, 179t Piperidine, ionization energy, 504i PIPES, 178t, 179t Pipet, 38–39 bulb, 38 calibration, 43 tolerance, 38t, 39t uncertainty, 63–64 pi-pi interactions, 621t PIPPS, 178t, 179t Piranha solution, 707 Piston pump, HPLC, 611, 611i Pitzer equation, 146, NR4 (7.7) Pixel, charge coupled device, 458 pK (pKa, pKb), 165 Gran plot, 217–218 principal species, 195–197 protein titration, 205b strong acids, 220b titration curve, 211i, 213i pKw, 165 0.1 M KCl, 272 Planck distribution, 449b Planck’s constant, 394 Plane angle, 14t Plane-polarized light, 394 Plankton, 536p Plant: 13 C isotopes, 509b phytoremediation, 252m pigment, 542m Plasma (blood): calcium, 330 definition, 401 drug analysis, 712 Plasma (ionized gas): 479b, 486–487, 490–491, 494, 502b Plasma wave, 465 Plasmon, 465 Plaster, 253b Plastic: bottle, 223, 492, 700, 700t digestion, 707 Plasticizer, 315i Plate height, 551, 559b, 593p, 597i, 651–652, 656 Plate number, 552, 597 Platform, L’vov, 484i Platinum: diaphragm, 317i electrode, 281, 309, 311, 313d, 367i, 616 embrittlement, 708 handling, 708 masking, 253 microelectrode, 384 potential range, 377t vessel, 706t, 707, 708 PLOT, 566m Plutonium, 302p Plutonium EDTA, 241 PNA (peptide nucleic acid), 465 Pneumatically assisted electrospray, 520i Pneumatic nebulizer, 482, 483i pn Junction, 333, 457 pOH, 164 Poisson distribution, 444p, NR13 (18.32) Polar, 236b Polar embedded group, 602, 646 Polarity, 569t, 572i Polarizability, 638m Polarizable electrode, 366 Polarization, 447 concentration, 365 Polarized light, 394 Polarogram, oscillation, 378m Polarographic wave, 378 Polarography, 376–378 apparatus, 377i ascorbic acid, 300i diffusion current, 378 dropping-mercury electrode, 376–378 half-wave potential, 300i, 378 oxygen waves, 378 polarographic wave, 378 residual current, 378 sampled current, 378 square wave, 379–380 wave shape, 379–380 Polar stratospheric clouds, 393b, 394 Pollution, 252m Polonium-210, 505 Polyacrylamide, 647, 648i, 658m Polyalkylamine ion exchanger, 636t Polybrene, 658, 658i Polybrominated diphenyl ether, 712 Polybutadiene, 556i Polychromatic light, 450m Polychromator, 457, 613i Polycyclic aromatic hydrocarbon, 413 Poly(diethylene glycol succinate), 557t Poly(dimethylsiloxane), 537b Polyether ether ketone (PEEK), 616 Polyethylene: bottle, 223, 700, 700t infrared cell, 399 Index membrane, 330, 399 vessel for HF, 707 Poly(ethylene glycol), 569t Poly (2-hydroxyethyl methacrylate), 328i Polyimide, 566 Polymer: conductive, 329m, 372b molecularly imprinted, 650b Polypeptide, 185b Polypropylene flask, 37i, 38 Polyprotic acids and bases, 133–136, 185, 194–195 fractional composition equations, 198m Polypyrrole, 372b Polysaccharide, 636, 637i Polysiloxanes, 569t Polystyrene, 471i, 599, 635, 635i, 636t, 647, 648i, 649i Polytetrafluoroethylene, see Teflon Polyunsaturated fat, 105i Poly(vinyl alcohol), 647 Poly(vinyl chloride), 315i, 327, 352b Ponceau, 438p Pooled standard deviation, 77 Poppy seed, 530 Population: inversion, 448 mean, 69 standard deviation, 69 Porcelain, 705 Pore size, 647, 650 Po River, 699b Porous carbon, 567i Porous graphitic carbon, 602 Porous-layer open tubular column, 566, 571 Porous plug, 317i, 320i Port, injection, 577i Post-column derivatization, 613 Postprecipitation, 679 Potassium: blood test, 323t diffusion coefficient, 551t EDTA titration, 254p gravimetric analysis, 675t ion channel, 236b ion-selective electrode, 329t precipitation titration, 693t reduction, 377 valinomycin complex, 315i Volhard titration, 693t Potassium bromate, 359p Potassium bromide: beam splitter, 471 infrared cutoff, 399m pellet, 399 Potassium chloride: density, 701 entropy of solution, 119 liquid junction, 314t salt bridge, 286 solubility, 122d Potassium cyanate, 678t Potassium dichromate: absorbance standard, 454t redox titrations, 351 spectrum, 398d Potassium dihydrogen citrate buffer, 320t Potassium hydrogen iodate, 222t Potassium hydrogen phthalate: density, 48p, 222t pH calculation, 192 pH standard, 320t primary standard acid, 222t, 235 Potassium hydrogen tartrate, 144, 320t Index Potassium hydroxide, 130t flux, 708t solution preparation, 223 Potassium iodate, 353 Potassium iodide, 707 Potassium nitrate, 143, 708 density, 701 Potassium perchlorate, 708 Potassium permanganate, 345d, 349–350 Potassium peroxydisulfate, 352b Potassium persulfate, 223 Potassium pyrosulfate, flux, 707, 708t Potassium tetraphenylborate, 675t, 693t Potassium tetroxalate buffer, 320t Potato chips, 717p Potential: cell membrane, 303p difference, 14t, 281 electric, 281 electrode conversion scale, 311 electrode range, 377t energy, 504b glass electrode, 318 half-cell, 290b, 291i ion-selective electrode, 315–317 ohmic, 364 scale, 311i standard, 287–288 zero charge, 379b Potentiometer, 284i, 286d, 313d Potentiometric titration: Gran plot, 346–347 precipitation, 312, 689i redox, 345d Potentiometry, 309, 362 Potentiostat, 366 Potomac River, 117b Pound, 15m, 15t, 16m conversion to newton, 160p Pound per square inch, 15t Powder, grinding, 705 Power: calculator, 61m electric, 282 uncertainty, 61–62, 62t units, 14t, 15t Power supply, 362i ppb, 19 ppm, 19 PQQ (Pyroloquinoline quinone), 374 Practical-grade chemical, 23b Precambrian age, 673b Precipitant, 675 Precipitate: composition, 679–680 electric charge, 692 Precipitation, 676–679 crystal growth, 676 digestion, 679 electrolyte role, 677–678 filterability of product, 676 homogeneous, 677, 678t product composition, 679–680 separations, 123 titration, 308b, 312, 685–692 Precision, 51b, 56 assessment, 99m atomic spectroscopy, 480, 494t combustion analysis, 685, 685t injection, 102 instrument, 102 interlaboratory, 102, 103b intermediate, 102 intra-assay, 102 standard deviation, 69m Precolumn (guard column), 610 Preconcentration, 484, 525, 584, 640, 699b, 713–714 Precursor ion, 524 Prefix (multiplier), 14–15 Pregnancy test, 432 Preheating region, 483i Premix burner, 482, 483i Preoxidation, 348 Preparation of sample, 584–586, 699–715, 699b Preparative chromatography, 547–548, 606b Preparing solutions, 19–20 Prereduction, 348 Preservative, 347, 354 Pressure: critical, 606t definition, 14m gas chromatography, 574 HPLC, 598, 598t, 618 programming, 574 units, 14, 14t, 15t water column, 670p Pressure broadening, 489 Primary amine, 132 Primary standard, 23, 23b, NR5 (10.18) acids and bases, 222t, 223 buffer, 262 elements, Appendix K Principal species, 195–197 Principle of Le Châtelier, 120–121, 143d, 172, 189b, 258b, 288, 493m Prism, 450, 465 Procion Brilliant Blue M-R, 169b Product, 20m Product ion, 524 Progestin, 79b Programmed temperature, NR18 (23.12) Proline, 187t Propagation of uncertainty, 57–64, App C, NR2 (3.3) addition and subtraction, 57–58, 62t calibration curve, 89 exponents, 62t logs, 62t mixed operations, 58 multiplication and division, 58, 62t standard addition, 108 systematic error, 62–64 Propane: hydration number, 142t thermal conductivity, 580t 2-Propanol: eluent strength, 604t ultraviolet cutoff, 604t 1-Propanol chromatography solvent, 610 “Proportional to” symbol, 376m Protein: aptamer assay, 433 charge ladder, 655, 671p colorimetric analysis, 87, 92p denatured, 664 digestion, 172i electron-transfer dissociation, 528–529 electrospray, 526–528 food, 27p isoelectric focusing, 200b Kjeldahl analysis, 223–225, 224b MALDI, 527b mass spectrometry, 526–529, 527b molecular mass, 526–528, 664 purification, 650 sequence, 502 sequencing, 528–529 structure, 185b titration, 205b transferrin, 401–403 weight percent nitrogen, 224b Protein A, 649 Proteomics, 528 Protic, 126 Protic solvent, 128 Protocol, 100 Proton, 126 mass, 508t Protonated H2O cluster, 529 Protonated methane, 505i Protonated molecule, 505, 522 Prototype kilogram, 14t Pseudostationary phase, 663 psi (pounds per square inch), 15t Pteropod, 189b Pt gauze electrode, 367i p-Type semiconductor, 332 Pulsed electrochemical detector, 616 Pulse height, 379i Pulse laser, 495 Pump HPLC, 611, 611i peristaltic, 427i syringe, 430, 431i Purge, septum, 577 Purge and trap, 586, 587i Purified grade chemical, 23b Purity: “nines” nomenclature, App K precipitate, 679 reagent, 23b PVC, 352b Pyrene, 444p Pyrex, 37m, 43 Pyridine, 140p, 212, 573t Pyridinium, 140p, 259 Pyridoxal phosphate, 166 Pyridylazonaphthol, 251i Pyrocatechol violet, 250t, 251i Pyroelectric effect, 459 Pyrogallol red, 251i Pyrolysis, 484, 684 Pyrolytic graphite, 484 Pyrophosphate, 681 Pyrophosphoric acid, 706t Pyrosulfate, flux, 708t Pyrrolidone, 714i Pyruvate, 298t QAE ion exchanger, 637t Q test, 83m Quadrapole ion guide, 525i Quadratic equation, 88b, 164m, 170 Quadrupole electric field, 515m Quadrupole ion-trap mass spectrometer, 515, 516 Quadrupole mass spectrometer, 513–514, 515, 516 Qualitative analysis, 9, 505 Quality assessment, 99b Quality assurance, 96–111, 100t Quality control sample, 99 Quantitation limit, 105m Quantitative analysis, Quantitative transfer, 7, 60b Quantum dot, 649 Quantum efficiency, 459 Quantum yield, 435, 437b Quartz crystal microbalance, 29b, NR1 (2.4) Quartz-halogen lamp, 446 Quasi-reference electrode, 383i Quaternary ammonium hydroxide, 130t I19 Quaternary ammonium ion exchanger, 636t Quenching, 412, 413i, 433–437, 443p, 462 Quercitin, 622 Quinhydrone electrode, 306p Quinone, 306p R2 correlation coefficient, 101 ␳ (resistivity), NR9 (14.37) Racemic mixture, 632p rad (radian), 14t Radian, 14t Radian-degree conversion, 461 Radiant flux, 14t Radiant power, 396m Radiationless transition, 406 Radiative heating, 449b Radioactivity, 673b, 674 Radio wave, 395i Radium, 674 Radium chloride, 674 Radius: hydrated, 142, 146 hydrodynamic, 653 ionic, 142b, 146 Radon, 673b Rain, acid, 258b, 268 Rainwater: alkanes, 19 H2O2, 376 pH, 130i, 322b Raman, C V., 411b Raman scatter, 411b Raman spectrum, 163b Ramp, voltage, 378, 379i Random error, 56 Random heterogeneous material, 12b Random sample, 12b Random variable, 558b Random walk, 408 Range, 102, 102m dynamic, 89, 102m linear, 89, 102m Rare earth, 479b Rat, 666i Raw data, 97 Rayleigh, Lord (J W Strutt), 76, 411b Rayleigh scatter, 411b RDX, 519i Reactant, 20m Reaction coil, 429m Reaction quotient, 120, 289 Readability of balance, 31 Reagent blank, 98, 402 Reagent evaporation, 223, 492 Reagent gas, 505, 518 Reagent grade chemical, 23b Receptor: affinity chromatography, 649 transferrin, 300–301 Rechargeable battery, 279b Reciprocal centimeter, 394 Reconstructed total ion chromatogram, 523, 523i Rectangular distribution, 62 Recycling, 31, 610m Red blood cell, 68b, 80 Redox indicator, 345–346, 346t Redox reaction, 280 balancing, App D Redox reagents, 341t Redox titrations, 340–356 calculating curve shape, 341–344, 345d cerium(IV), 350–351 dichromate, 351 I20 end point, 344 Gran plot, 346–347 indicators, 345–346 iodine, 351–356 permanganate, 349–350 preoxidation, 348 prereduction, 348 procedures, NR9 (15.2) spreadsheet, 344m superconductor, 340b, 355b, 359p Reducing agent, 280 Reducing strength, 288t Reductant, 280 Reduction, 280 Reduction catalyst, 684m Reduction potential: acid dissolution, 706 electron flow, 291i Latimer diagram, 292b relation to K, 293 standard, 287 tables, App H transferrin, 300–301 use of tables, 288 Reductor, 348 Referee, 509i Reference cell, 446, 460b Reference cuvet, 399 Reference electrode, 309–311, 366 calomel, 310, 311i, 342i conversion scale, 311 glass electrode, 690i silver-silver chloride, 310, 311i symbol, 366i 3-electrode cell, 366 Reference material, 98, 102 Reflection: attenuated, 464 grating, 446i, 447i, 451 total internal, 462 Reflectron, 514i, 515 Reflux cap, 709i, 710i Refraction, 450, 461 Refractive index, 394, 461, 461m detector, 612t, 616 fused silica, 477p Refractory element, 483 Refractory material, 707 Regression (least squares): linear, 83–91 multiple linear, 110–111 nonlinear, 272–274 Rejection of data, 83 Relative humidity, 49p Relative migration time, 664 Relative reference, 46 Relative retention, 545, 546, 553 Relative standard deviation, 69 Relative uncertainty, 56 Releasing agent, 493 Remediation, 340m Renal function blood test, 323t Replicate measurement, 11, 704 Reporting limit, 105 Reporting results, 11 Reprecipitation, 679, 696p Representative sample, 12b, 699, 699b, 700 Reproducibility, 102 Residence time, 483 Residual current, 367, 378 Residual sodium carbonate, 216b Resin, 543m, 635, 636m, 639 preconcentration, 714 Resistance: electric, 14t, 282 glass electrode, 318 pH meter, 293b superconductor, 340b units, 14t Resistivity, 332, NR9 (14.37) water, 641 Resolution: capillary electrophoresis, 651–652 chromatography, 548–549, 553, 617, 621m, 627, NR17 (22.13) electrophoresis, 657 FTIR, 470 gas chromatography, 567, 567i, 568i, 575, 588m mass spectrometry, 506m, 514, 516 monochromator, 493i spectroscopy, 452 Resolving power, 506, 514, 516 Resonant ion, 513i Respiration, 297 Respirator, 30 Response factor, 109, 580 Results, 11, 97 Retardation, 468, 470 Retention factor, 545, 545m, 546, 567, 617 average, 625b Retention gap, 576 Retention index, 573 Retention time, 545 Retention volume, 545, 547 Retina, 456b Retinal, 456b Retinol, 341t Revelle, R., Reverse bias, 333 Reversed-phase chromatography, 603, 604b, 609i, 617–628 column capacity, 548 Reverse osmosis, 641 Reversible electrochemical reaction, 382 Rhodamine G, 408 Rhodopsin, 456b Riboflavin, 298t, 413 Ribonuclease, 205b, 551t, 602i Ribose, 661i Ribosome, 528 Richards, T W., 674 Rich flame, 483, 493 Ring-down spectroscopy, 445b, 476p Rings plus double bonds, 510 Ritalin, 633p River: bicarbonate content, 153b calcium content, 153b lead analysis, 96 RMS noise, 472 RNA (ribonucleic acid), 205b, 380t, 419b, 433 Robotic arm, 308b Robustness, 105 Rock, 685 Rod cell, 456b Root, uncertainty, 61, 62t Root-mean-square (rms) noise, 472, NR15 (20.19) Ross electrode, NR8 (14.19) Rotating disk electrode, 374–376, 375i, 376i, 391p Rotational energy, 405 Rotational transition, 406, 410 Rounding-off rules, 53 Round-robin, 56m, 685t Ru(II): luminescence, 433, 436–437, 443p, 462 sensitizer, 434b upconversion, 437b Rubber: glove, 30 policeman, 40 semipermeable membrane, 329 Rubidium hydroxide, 130t Rubidium sulfate, 581 Ruggedness, 102, 617 Rule of three, 619m, 633p Run buffer, 657 Ruthenium tetroxide, 706 Rutherford, E., 673b Rutin, 622 s (second), 13, 14t s (standard deviation), 69, 77, 86 sr (steradian), 14t ␴ (population standard deviation), 69 ⌺ (summation sign), 69 Safety, 30–31 Safety glasses, 30i Safranine T, 298t Salicylaldoxime, 676t Salicylate, 680 Salicylic acid, 166, 632p Saliva pH, 130i Salmonella enterica, 237 Salt, 122m, 126 Salt bridge, 285, 286d, 293b Salting out, 159p, 650 Sample: cell, 460b composite, 12b digestion, 708 dissolution, 705–710 injection (chromatography), 577–579, 589, 611, 612i loop, 611, 612i preconcentration, 714 preparation, 6, 7, 11, 525, 584–586, 699–715, 699b random, 12b selection, 11, 12b, 700 size for analysis, 703 storage, 700 Sampled current polarography, 378 Sampling, 6, 11, 699 constant, 703 direct solid, 485 drugs in river, 699b references, NR22 (27.1), NR22 (27.8) representative sample, 12b statistics, 701–705 time, 378i trace elements, 497b variance, 701 Sandwich: complex, 373m injection, 577, 577i San Francisco Bay, 236 Sanger, F., 674m Sapphire, 399m, 460b, 611 Saturated calomel electrode, 310, 311i Saturated fat, 105i Saturated solution, 121 Saturation fraction, 425 Scale, 253b Scale up: chromatography, 547–548, 596–597 gradient, 625b Scandinavia, 479b Scanning tunneling microscope, 283b Scatchard plot, 424–425 Scattering, 411b S.C.E (saturated calomel electrode), 310, 311i Index Schematic circuit diagram, 282i Schlieren, 37 Scifinder, 6m SCOT, 566m Scripps Institution of Oceanography, Seawater: ammonia, 429 carbon dioxide, 440p graphite furnace atomic spectroscopy, 485 iron, 381i pH, 130i phosphate, 679i salt concentration, 17 trace metals, 640, 718p Second, 13, 14t Secondary amine, 132 Second derivative, 217 Second-order diffraction, 411b, 451 Sediment, 485, 699, 700i Segmented gradient, 608i, 623, 625 Segregated heterogeneous material, 12b SE ion exchanger, 637t Selected ion chromatogram, 523 Selected ion monitoring, 522–523, 523i, 582, 583i Selected reaction monitoring, 524–526, 583 Selection of sample, 11, 12b, 700 Selectivity, 98 Selectivity coefficient: fixed interference method, 324b ion exchange, 637 ion-selective electrode, 324, 324b, 328, 329t matched potential method, 324b separate solution method, 324b, 339p Selenite, 412 Selenium: blood, 496 fluorescence assay, 412–413 isotopes, 497 Self-absorption, 412, 413i, 494 Semiconductor, 332, 459 Semipermeable barrier, 286d Semipermeable membrane, 329, 665, 677d Semithymol blue, 440p Sensitivity, 98 balance temperature coefficient, 34 gas chromatography, 580t Sensitizer, 434b Sensor: attenuated total reflectance, 463–465 biosensor, 372, 419 carbon dioxide, 440p DNA microarray, 413 electrochemical, 308b electronic nose, 372b fluorescence resonance energy transfer, 419 glucose, 372–376 luminescence, 413, 433 nitrate, 700i nitrite, 477p null position, 33 optical, 461–467 optode, 462 oxygen, 371b, 433i, 436 ozone, 55b quartz crystal microbalance, 29b solid state, 331–334 surface plasmon resonance, 465–467 Separate solution method (selectivity coefficient), 324b Index Separation factor, 545, 657 Separations, 537–559, 565–589, 596–628, 634–667 adsorption chromatography, 543 affinity chromatography, 543, 649–650 anions, 641 capillary electrophoresis, 650–667 cations, 641 chromatography, 543 controlled-potential electrolysis, 368 enantiomers, 570b, 629p, 630p, 631p, 641, 649–650, 663i, NR19 (25.3) gas chromatography, 565–589 gel filtration, 543, 647–649 gel permeation, 543, 647–649 high-performance liquid chromatography, 596–628 hydrophobic interaction, 650, 651i ion chromatography, 642–645 ion-exchange chromatography, 543, 635–641 isotopes and isotopic molecules, 533i, 601b, 662i molecular exclusion, 543, 647–649 molecularly imprinted polymer, 650b optical isomers, 547 partition chromatography, 543 pharmaceuticals, 547 precipitation, 123 preparative, 606b selecting HPLC separation mode, 607–609 size exclusion, 543, 647–649 solvent extraction, 538–541 Separator column, 642 Sephadex, 636, 637i, 647t Septum, 566, 577 purge, 577i, 578 Sequencing: DNA, 664 Protein, 528–529 Sequential injection, 430, 431i, 464–465 fiber optic spectrometer, 462–463 Series expansion, 412m Serine, 187t Serum, 401, 713 Serum albumin, 200b, 441p, 551t, 656 Serum iron determination, 401–403 Seven coordination, 239i, 241i Sewage, 525–526, 699b Sewage treatment, 117b Shatterbox, 705, 706i S.H.E (standard hydrogen electrode), 287 Sheath liquid, 521 Shell, 189b, 495i Shorthand (organic structures), 136 Shot noise, 473 Shower, 30 Sialic acid, 639i, 640 Siderocalin, 237 Siderophore, 239i Siemens, 283b Sieve: mesh size, 572, 702t molecular, 571 Sieving, 664 Sigma bonding electrons, 504, 504i Sigma orbital, 404 Sign convention for current, 362, 376 Signal: averaging, 472 detection limit, 103 integration, 463 Signal-to-noise ratio, 458i, 459, 472, 492i monochromator, 452 Significance test, 79 Significant figure, 51 addition and subtraction, 52–53 graphs, 54 laboratory work, 59 least-square parameters, 86 logarithms and antilogarithms, 53–54 mean and standard deviation, 70 multiplication and division, 53 real rule, 59 zeros, 52 Silanization, 558 Silanol, 568, 599, 600m, 653 pKa, 658i Silica: acidity, 201 aminopropyl, 670p capacity, 548 capillary preparation, 657 chromatography, 8, 599–601, 599i, 647 ethylene bridge, 599 fluorescent beads, 436, 437i fused, 399, 566 gel, 41t, 408 grating protective layer, 451 hydrolysis, 601 monolithic column, 601b pKa, 658i stationary phase, 621t stationary phase for high pH, NR18 (24.10) surface charge, 658, 658i Silicate, 318i, 685, 706, 707 Silicon: charge coupled device, 458–459 isotope abundance, 508t photodiode array, 457 photoresponse, 455i semiconductor, 332 structure, 332i Silicon carbide, 485, 685 globar, 447 Silicon chip chromatography, 574, 576b Silicon dioxide, 333 Silicone breast implant, 537b Silicone rubber, 371b Silicon nitride, 334i, 685 Silicon tetrafluoride, 685 Siloxane, 537b, 569t, 599i, 601 SI units, 13–16 Silurian age, 673b Silver: bromide, 326t coins, 18 cyanide equilibria, 275p, 276p EDTA titration, 252 electrode, 311–312, 690i field effect transistor, 333–334 iodide, 326t ion-selective electrode, 326, 329t masking, 253 permanganate titration, 349t reducing agent, 348 stripping analysis, 380t sulfide, 326, 326t thiocyanate, 326t vessel, 706t, 707 waste recycling, 31 Silver(II), 348, 370 Silver bromide, 334 Silver chloride: colloidal particle, 678i electric charge, 692 equilibria, 137p infrared window, 399m ion-selective electrode, 326t light sensitivity, 692 solubility in KCl, 319 Silver-silver chloride electrode, 310, 311i combination electrode, 317 Simplex optimization, 110, NR3 (5.13) Simulation of chromatography, 625–628, NR17 (23.1), NR18 (23.25), NR19 (24.37), NR20 (25.6) Simultaneous equations, 422–423 Single-beam spectrophotometer, 396i, 399, 445 Single-column ion chromatography, 645 Single-molecule spectroscopy, 408 Singlet state, 404, 436, 437b Sintering, 434b Size: ion, 637 mesh, 572 nebulizer droplets, 483i sieve, 572 Size exclusion chromatography, 543, 647–649 Skimmer cone, 520i, 521 Skin cancer, 14 Slit, monochromator, 446i, 447i Slope, App B least-squares calculation, 84, 86 titration curve, 216–217, 687 SLOPE, 85 Slurry, 7, 40 Smith, G E., 458m Smith, John, 51b Smoke, 336p, 715 Snail, 189b Snell’s law, 461 Snow, 500p, 642m Soap, 253b Soddy, F., 673b Sodium: critical care profile, 323t diffusion coefficient, 551t dispersion, 697p D line, 461 error, 320, 321i ion channel, 236b ion-selective electrode, 324b, 329t mobility in glass, 318 vision, 456b Sodium aluminosilicate, 571i Sodium amide, 234p Sodium azide, 605i Sodium bismuthate, 348 Sodium bisulfite, NR5 (8.12) Sodium borate, flux, 708t Sodium carbonate: flux, 708t primary standard, 222t, 235 residual, 216b titration, 233p Sodium chloride: infrared cutoff, 399m ion pair, 145b liquid junction, 314t matrix, 485 ocean, 17 Sodium dodecyl sulfate, 442p, 662, 662m, 664, 671p gel electrophoresis, 664i Sodium hydrogen sulfite, 31 I21 Sodium hydroxide: equilibrium, 139p flux, 708t preparation, 223 reaction with glass, 223 standardization, 235 strong electrolyte, 130t Sodium hypochlorite, 27p, 173 Sodium metabisulfite, NR5 (8.12) Sodium nitrate in HPLC, 617 Sodium octyl sulfate, 669p Sodium oxalate, 350 Sodium peroxide, flux, 707, 708, 708t Sodium peroxyborate, 358p Sodium sulfate ion pair, 145b Sodium tetraphenylborate, 676t, 695p Sodium thiosulfate, 353–354, NR10 (15.24) Soft drink, 10t, 464 Soil, 252m, 432, 710–711 Mars, 308b, 323, 328b Solar energy, 434–435b, 449b Solar thermal electric power, 435b Solid, standard state, 118 Solid angle, 14t Solid-gas adsorption chromatography, 566 Solid-phase extraction, 524, 699b, 713–714 disk, 714 Solid-phase microextraction, 584–585, 586 Solid sampling, 485 Solid-state chemical sensor, 331–334 Solid-state ion-selective electrode, 329m Solid-supported liquid-liquid extraction, 712, 713i Solomon, S., 394 Solubility: calcium carbonate, 189b, 203p calcium sulfate, 155–157 common ion effect, 122–123 complex ion formation, 125i Eº, 294 gas (Henry’s law), 139p, 202p203p ionic-strength effect, 143–144 ligand-concentration effect, 125i lithium fluoride, 160p magnesium hydroxide, 157–158 metal complexes, 540–541 minerals, 268 separations, 123 solubility product, 121, 294, App F Solubility product, 121–124 hydroxides, 131t Solute, 16 polarity, 569t standard state, 118 Solution preparation, 19–20 Solvation, 409 Solvent, 16 additive (HPLC), 610 chromatography, 603, 604t, 605m, 610 front, 614 gradient, 623–625 pool, 604b sample, 610, 611i standard state, 118 trapping, 578 triangle, 619i, 620i water content, 610 Solvent Blue 2, 531 Solvent-bonded phase interface, 604b I22 Solvent extraction, 538–541 crown ether, 542b distribution coefficient, 539, 541 dithizone, 540d, 541i efficiency, 538–539 metal chelator, 540–541, 540d, 542b partition coefficient, 538 strategies, 541 SOLVER, 261–262, 273–274, 421 Sorbent bead, 464 Sørensen, S P L., 129m, 172m Source: field effect transistor, 333 infrared, 460b spectrophotometer, 447–450 South Pole, 15i Space charge, 516 Spacecraft, 15m, 308b, 665m Space focus plane, 514i, 515 Space shuttle, 303p Sparging, 610m Sparkman, O D., 507m Speciation, 197 Species, 11m Specific adsorption, 379b Specification, 97, 100t Specific gravity, 18m Specificity, 98, 101 Spectra, 397m Spectral interference, 493 Spectral width, FTIR, 470 Spectrometer, ion mobility, 518 Spectronic 20 spectrophotometer, 52 Spectrophotometer, 445–460 atomic absorption, 481i atomic spectroscopy, 488–493 cuvet, 399 detector, 454–461 diode array, 400i dispersive, 457 double-beam, 400, 446 emission, 410i fiber-optic, 462–463 filter, 454 Fourier transform (FTIR), 467–472 light sources, 447–450 low noise, 473–474 monochromator, 450–454 noise, 473–474 optical train, 446i, 447i photodiode, 457 precision, 400i single-beam, 396i, 399, 445 source noise, 473 Spectronic 20, 52 stray light, 453–454 Thermo Evolution 600, 447i Varian Cary 3E, 446i Spectrophotometric titration, 403, 427i Spectrophotometry, 394 absorption of light, 395–399, 398d accuracy, 400 analysis of mixture, 419–423 Beer’s law, 396, 397b, 419 detectors, 454–461 dispersion, 452 double-beam, 446i, 447i emission, 395i, 398d, 406–407, 408–413 equilibrium constant measurement, 424–425 errors, 400 flow injection analysis, 427–429 fluorescence, 398d, 406–407, 408–413 Fourier transform, 467–472 grating, 450–453 isosbestic point, 423, 439p Job’s method, 425 luminescence, 408–413 measuring EЊЈ, 301i method of continuous variation, 425–427 ozone monitor, 55b phosphorescence, 406–407 properties of light, 394–395 resolution, 452 Scatchard plot, 424–425 sequential injection, 430 serum iron determination, 401–403 signal averaging, 472 time-resolved fluorescence, 432 titration, 427i Spectroscopy, single molecule, 408 Spectrum: absorption, 397, 398d attenuated total reflectance, 464–465 blackbody, 449b corrected, 461i electromagnetic, 395, 395i emission, 410, 411b excitation, 410 uncorrected, 461i Speed of light, 13m, 394, 468m Sphalerite, 257p Spherogel, 648i Spike, 98, 102, 525, 536p recovery, 98 Spiking, 579 Spills, 30 Spin angular momentum, 437b SP ion exchanger, 637t Spleen, 650 Split injection, 577, 578i, 589 Splitless injection, 578–579, 589 Split peaks (chromatography), 610 Split point, 577i Split ratio, 577 Split vent, 578i Spontaneous reaction, 294m Spreadsheet: ABS, 78i absolute reference, 46 acid-base titration, 226–229, 228t Add-Ins, 82 Analysis Tool Pack, 82 arithmetic operations, 45 ASIN, 461 auxiliary complexing agent, 256p AVERAGE, 70 BINOMDIST, 594p binomial distribution, 594p books, NR2 (2.25) cell, 43 Chart, 46–47, 66p, 89–91 circular reference, 161p, 278p complex formation, 245–246, 256p confidence interval, 75 COUNT, 75 Data Analysis, 82 DEVSQ, 89 documentation, 45 EDTA titration, 245–246 error bar, 90–91 FINV, 81t formula, 45 function, 45 GOAL SEEK, 158, 181 graphing, 46–47, 66p intercept, 86–87 INTERCEPT, 85 introduction, 43–46 iteration, 161p label, 45 least squares, 89–91, 110–111, 272–274, NR2 (4.6) LINEST, 86–87, 101, 110i, 111 matrix, 86–87 matrix functions, 422–423 MINVERSE, 423 MMULT, 423 naming cells, 181 NORMDIST, 71–72 number, 45 order of operations, 45 parentheses, 45 pooled variance, 82 precipitation titrations, 690–691, 698p redox titrations, 344m relative reference, 46 slope, 86–87 SLOPE, 85 SOLVER, 261–262, 273–274, 421 solving linear equations, 422–423 SQRT, 75i standard deviation, 70 STDEV, 70 TINV, 75 Trendline, 89 t test, 82–83 variance, 82–83 SQRT, 75i Square wave polarography, 379–380 Squaric acid, 132b Stability constant, App I cell voltage, 296–297 EDTA complexes, 242t Stacking, 659–660 Stadium analogy for luminescence, 408 Staircase: voltage ramp, 378, 379i wave, 379i Standard, 83 acids and bases, 235 analytical, App K elemental assay, App K matrix matched, 495 matrix matching, App K NIST traceable, App K pH, 320t solution, 9, 23, 87, 492 state, 118, 119f stoichiometry, App K ultraviolet absorbance, 454t ultraviolet/visible wavelength, NR14 (19.10) Standard addition, 102, 106–108, 114p, 115p, 330–331, 336p, 338p, 381i, 392p, 418p, 493, 494i, 496, 500p, 501p, 585, 586 Standard curve, Standard deviation, 10, 69, 72, 75, 77, 79 additivity, 554m binomial distribution, 701 chromatography, 558b diffusive broadening, 551 F test, 80–81 least squares parameters, 86–87 measure of experimental error, 57 pooled, 77 rectangular distribution, 63 sampling, 701–705 standard deviation of the mean, 72 triangular distribution, 63–64 Standard enthalpy change, 119 Standard HCl, 222t, 233p, 235 Standard hydrogen electrode, 287 Standardization, 23, 235 Index Standard operating procedure, 99 Standard reduction potential, 287, 290b equilibrium constant, 293 Latimer diagram, 292b measurement, 305p relation to equilibrium constant, 293 tables, App H use of tables, 288 Standard Reference Material, 56, 102, NR2 (3.1) Stannic chloride, 706 Stannous chloride, 348, 482b Stannous ion, 341t Starch, 347, 351 Static electricity, 282i Stationary phase, 542 bonded, 568 chiral, 629p, 630p, 631p gas chromatography, 568, 569t HPLC, 621t ion exchange, 635–636 liquid chromatography, 599–602 molecular exclusion, 647, 648i solvent interface, 604b Statistics, 68–91 1-tailed test, 82 2-tailed test, 82 comparison of means, 76–80 confidence interval, 73–75 detection limit, 103–105 F test, 80–81 Gaussian distribution, 68–73 Grubbs test, 83 least-squares, 83–91 linear regression, 83–91 multiple linear regression, 110–111 nonlinear regression, 272–274 rejection of data, 83 sampling, 701–705 standard deviation, 79, 85–86 Student’s t, 73–80, 82–83 STDEV, 70 Stearic acid, 105i Steel mortar, 705 Stefan-Boltzmann constant, 448b Step height, 378i Steps in chemical analysis, 11 Stepwise formation constants, 124b, App I Steradian, 14t Stern layer, 379b Stern-Volmer equation, 436 Steroid, 713 Stimulated emission, 448 Stir-bar sorptive extraction, 586 Stirring bar, 22i Stirring motor, 22i Stochastic theory, 558b Stoichiometry, 21–22, 21m, 425–427 standards, App K Stokes equation, 653 Storage: dilute solutions, 331m sample, 700 Storage bottles, 700t St Paul’s Cathedral, 258b Straight line graph, 83–91, App B Strata, 673b Stratosphere, 393b Stray light, 453–454, 463 Streamlined calculation, titration, 686–687 Streptavidin, 466 Streptomyces pilosus, 238b Stretching, molecular, 405i Strip chart recorder, 460b Stripping analysis, 380–382 Index Strong acid, 130–131 pH calculation, 163–165 reaction with weak base, 174b titration of strong base, 206–208 titration of weak base, 210–212 Strong base, 130–131 pH calculation, 163–165 reaction with weak acid, 174b titration of weak acid, 208–210 titration with strong acid, 206–208 Strong electrolyte, 16m Strongly acidic ion exchanger, 635, 636t Strongly basic ion exchanger, 635, 636t Strontium, 349t, 493–494 Strontium aluminate, 407 Strontium hydroxide, 131t Strutt, J W., 76, 411b Strutt, R., 673b Student (W S Gosset), 73m Student’s t: comparison of means, 76–80, 82–83 confidence interval, 73–75 table, 73t Styrene, 635i Sublimation, 606b Substituent, 185b, 186 Subtraction, 62t significant figures, 52–53 uncertainty, 57–58 Successive approximations, 156m, 191b Succinate, 146, 298t Succinic acid, 138p Sucrose: chromatography, 542m diffusion coefficient, 551t electrophoresis, 661i Sugar, 27p, 266, 354t, 361b, 570b, 646i, 661i colorimetry, 394 Sulfamic acid, 28p, 222t, 678t Sulfanilic acid, 416p, 440p Sulfate: acid mine drainage, 130i copper equilibria, 277p, 278p EDTA titration, 253 formal potential, 298t gravimetric analysis, 675t homogeneous precipitant, 678t Mars, 308b precipitation titration, 693t salting out, 650 Sulfide: EDTA titration, 253, 257p gas trapping, 715t homogeneous precipitant, 678t ion-selective electrode, 326, 326t precipitation titration, 693t volatility, 706 Sulfite: ammonia analysis, 429 analysis, 715t buffer demonstration, 176d clock reaction, 176d food, 359p formal potential, 298t reductant, 341t wine, 390p Sulfonic acid, ion exchange, 636t Sulfosalcylic acid, 222t Sulfur: analysis, 683–685, 697p atomic emission, 488, 490 combustion analysis, 683–685 detection, 616 detector, 580t, 582, 582i flame photometric detector, 587 isotope abundance, 508t Sulfur chemiluminescence detector, 580t, 582, 582i, 587 Sulfur dioxide: acid rain, 268, 322b blood test, 323t electrode, 330 emissions, 258b food preservative, 390p gas trapping, 715t iodimetric titration, 354t Karl Fischer titration, 385 prereduction, 348 reductant, 341t trapping gas, 715t Sulfur hexafluoride, 5, 606t, 607b Sulfuric acid: acid rain, 322b digestion, 223, 706t, 707 drying agent, 41 strength, 130t, 220b–221b Sulfurous acid, 322b Sulfur oxides, 322b, 684 Summation sign, 69 Sun, 447, 448b Sunset yellow, 438p “Super acid,” 220b Superconductor, 340b, 355b, 359p, 360p, 493i, 696p Supercritical fluid, 606b chromatography, 606b extraction, 711–712, 711i Superficially porous particle, 602 Supernatant liquid, Supernate, 402m Supernova, 542b Supersaturation, 676 Support-coated open tubular column, 566, 566i Supporting electrolyte, 378 Suppressed-ion chromatography, 642–645 Suppressor column, 642–643, 644 Surface acidity, 201 Surface plasmon resonance, 465–467 Surface tension, 482m, 521, 645b Surfactant, 540d, 616, 645, 645b, 658, 663, 665 Suspension, 676 Sustained-release drugs, 641 Sweeping, 663 Sweep rate, cyclic voltammetry, 383 Swiss Federal Institute of Technology, 328i Symbol: approximately, 21m approximately equal to, 16m electrodes, 366i implies that, 20m proportional to, 376m Symmetric bend, 405i Symmetric stretch, 405i Synapse, 456b Synge, R L M., 543m Syringe: blunt, 612m Hamilton, 39i HPLC, 612m microliter, 39 pump, 430, 431i sandwich injection, 577, 577i Systematic error, 55, 56, 322b Karl Fischer titration, 386 propagation of uncertainty, 62–64 Systematic treatment of equilibrium, 150–158, 258–270 precipitation titration, 690–691 strong acids and bases, 164–165 strong base, 164 weak acid, 167 Système International d’Unités, 13 T (tera), 15t Tailing, 558, 559i, 567, 600i, 603, 610 Tails (significance test), 79, 80i Tanaka, K., 519m Tap water, see Drinking water Tare, 31 Target value, 99b Tartaric acid, 246m, 259 Tartrate, 144, 641m Tartrazine, 438p, 677d Taste masking, 641 Taylor cone, 520i TC (to contain), 37 TCNQ, 417p TD (to deliver), 37 Tea, 10t TEAE ion exchanger, 637t Technical-grade chemical, 23b TEEN, 178t, 179t Teeth, 479b, 482b Teflon: bomb, 412, 707, 707i, 709 bottle, 700 chromatography support, 571 compound electrode membrane, 329 membrane desolvator, 486i, 487 stirring bar, 22i structure, 138p tube, 477p vessel, 496, 706t, 707 TEMN, 179t Temperature: atmospheric history, 5, 5i atomic spectroscopy, 487–488 buffer, 177–180, 178f, 320t capillary electrophoresis, 654, 657 chromatographic column heating, 598 chromatography, 556, 573–574, 599, 621 critical, 606t earth, 449b effect on balance, 34 effect on Kw, 129t equilibrium constant, 121 flame, 483t gravimetric analysis, 676 molarity of solution, 17, 42 ocean, 536p, 595b pH measurement, 321 plasma, 486i programming, 573–574 thermal conductivity detector, 580–581 units, 14t, 15t volume of glassware, 42–43 volume of water, 43 Temperature programming, NR18 (23.12) Template, 650b Temporary hardness, 253b Tenax, 586m Tera, 15t Terbium, 407b, 613 Terrestrial diet, 565b Tertiary amine, 132 TES (N-tris(hydroxymethyl) methyl-2-aminoethanesulfonic acid), 179t I23 Tesla coil, 486 Testosterone, 380t Tetraalkylamonium salt, ion pair, 169f Tetraborate, 707 Tetrabromofluorescein, 693m Tetrabutylammonium hydroxide, 130t, 225–226 Tetrabutylammonium ion, 646i Tetrabutylammonium salt, ion pair, 169f Tetracyanonickelate, 252 Tetracyanoquinodimethane (TCNQ), 417p Tetradentate ligand, 237 Tetraethylammonium salt, ion pair, 169f N, N,NЈ,NЈ-Tetraethylethylenediamine dihydrochloride, 178t N,N,NЈ,NЈ-Tetraethylmethylenediamine dihydrochloride, 179t Tetrafluoroethylene, see Teflon Tetrahydrofuran: eluent strength, 604t, 621i HPLC solvent, 618 mass spectrometry, 616 storage, NR19 (24.32) ultraviolet cutoff, 604t Tetrakis [3,5-bis(trifluoromethyl) phenyl] borate, 327 Tetramethylammonium hydroxide, 140p Tetramethylammonium salt, ion pair, 169f Tetramethylrhodamine, 162b Tetraphenylarsonium chloride, 676t Tetraphenylborate, 254p, 315, 315i, 675t, 676t, 693t Tetrapropylammonium hydroxide, 640 Tetrapropylammonium iodide, 640 Tetrapropylammonium ion pair, 169f Tetrathionate, 303p, 353 TEX86, 595b Thalassemia, 238b Theobromine, 6, 10t Theoretical performance of column, 593p Theoretical plate, 551, 559b, 597, 598t, 651–652, 656 Thermal cell, 399i Thermal conductivity, 580 definition, 580t detector, 580–581, 580t, 587, 589t, 684 Thermal desorption, 586 Thermal expansion, 17, 42–43 Thermistor, 332i Thermocouple, 459 Thermodynamic data, NR3 (6.5) Thermodynamic prediction, 121 Thermodynamics, 121 electrochemical cell, 306p Thermogravimetric analysis, 680, 696p Thermo Scientific Evolution 600 spectrometer, 447i Thick-film column, 588t Thin-film column, 588t Thin-layer chromatography, Glossary, Color Plate 28 Thioacetamide, 226m, 678t Thiocyanate: Fe(III) complex, 143, 143d, 442p gravimetric analysis, 675t ion-selective electrode, 326t iron complexes, 276p precipitation titration, 693t protein solubility, 650 Volhard titration, 692 Thioglycolic acid, 354t, 401 I24 Thiol, 283b Thiopental, 672p Thiosulfate, 303p, 341t, 353–354 anhydrous standard, NR10 (15.24) Thiourea, 253, 402 Thorium, permanganate titration, 349t Three-dimensional quadrupole ion trap, 515–516, 526 Threonine, 187t Thymol, 347 Thymol blue, 219, 221t, 440p Thymolphthalein, 221t Thymolphthalein complexone, 251i Thyroglobulin, 670p Time, 14t Time-of-flight mass spectrometer, 510, 514–515, 527b Time-resolved fluorescence immunoassay, 432 Tin: capsule for elemental analysis, 684 flame photometric detector, 587 food content, 501p gravimetric analysis, 675t iodometric titration, 354t reductant, 341t underpotential deposition, 369 Tin can, 501p Tin chloride, 348 Tin(II) chloride, 348, 482b Tin(IV) chloride, 706 TINV, 75 Tiron, 251m Tiselius, A., 651 Titanium: gravimetric analysis, 675t masking, 253 permanganate titration, 349t Titanium(III), 370 Titanium(IV) spectrum, 420i Titanium dioxide: photochemical oxidation, 352b, 391p photoelectrochemical cell, 434b Titanocene dichloride, 501p Titrant, 22 Titration, 22 acid-base, 205–229, 317m acid-base spreadsheet, 226–229, 228t argentometric, 692 autotitrator, 215 auxiliary complexing agent, 248–249 back, 252 blank, 23 blurred end point, 214 calculation for redox titration, 341–344, 345d cerium(IV), 350–351 complexometric, 239, NR6 (11.16), NR6 (11.21) dichromate, 351 diprotic system, 212–215 direct, 23, 251–252 displacement, 252 EDTA, 240–253, 427i EDTA end point, 249–251 effect of concentration, 211i end point, 22, 214, 249d, 427i, 687, 692 error, 23 Fajans, 692, 693t glass electrode, 317m Gran plot, 346–347 gravimetric, 24 history, NR22 (26.1) indirect, 252–253, 351 iodine, 353, 354t, 356t Karl Fischer, 385–386 Mars, 308b mass, 37, NR1 (2.16) microscale, 37 mixture, 689–690 nonaqueous, 225–226, NR6 (10.27) permanganate, 349–350 pK effect, 211i, 213i potentiometric, 341–344, 345d, 689i precipitation, 308b, 685–692 primary-standard acids and bases, 222t, 223 principles, 22–24 procedure, 36 protein, 205b redox, 340–356, NR9 (15.2) redox indicators, 345–346 spectrophotometric, 403, 427i stoichiometry calculations, 24 sulfate, 308b Volhard, 692, 693t weak acid-strong base, 208–210 weak acid-weak base, 226–229 weak base-strong acid, 210–212 Titration curve acid-base, 205–229, 270 derivative, 207i, 208, 211i, 216–217 difference plot, 270 EDTA, 243–249 precipitation, 685–690 redox, 340–356 spectrophotometric, 403–404, 427i Titrator, 36, 36i, 215 tm (chromatography), 617 TNT, 419b, 443p, 519i ␣-Tocopherol, 341t To contain (TC), 37 To deliver (TD), 37 Tolerance, 34, 42 buret, 35t micropipet, 39t pipet, 38t volumetric flask, 37t weights, 34t Toluene: eluent strength, 604t ultraviolet cutoff, 604t use, 538f Tomato juice pH, 130i Ton, 15t Tongs, 708 Tooth: atomic analysis, 479 decay, 266 enamel, 114p Torch, plasma, 486 Torr, 15t Total carbon, 352b Total internal reflection, 462 Total organic halide (TOX), 388p Total oxygen demand, 352b TOX, 388p Toxin immunoassay, 432 Trace, 11 Trace analysis, 23b, 497b, 640, 700 Trace-metal-grade chemical, 23b Trace-metal-grade HNO3, 496 Trace metals in snow, 500p Trans fat, 105 Transfer pipet, 38 Transferrin, 200b, 255p, 300–301, 401, 403, 417p, 438p, 501p, 639i, 640 electrospray, 526i Transformer oil, 385 Transfusion, 238b Transistor, 332i, 333–334 Transition: electronic, 404 rotational, 406, 410 vibrational, 406 Transition range: acid-base indicator, 219–223, 221t redox indicator, 345–346, 346t Transmission quadrupole mass spectrometer, 513–514 Transmittance, 396, 397b, 445 Spectronic 20 scale, 52i Transversely heated furnace, 484 Trap, mercury, 482b Treated data, 97 Trendline, 89 Triangle, lab, 708 Triangle, solvent, 619i, 620i Triangular distribution, 63–64 Tricapped trigonal prism, 242i Trichloroacetic acid, 401 Trichlorotrifluoroethane, 604t TRICINE, 178t, 179t Triethanolamine, 246m, 253 Triethylamine, 600i, 610, 617 Triethylammonium acetate, 610 Trifluoroacetic acid, 132b, 220b, 600i Trigonal prism, 242i Triiodide, 351 Trimethylammonium chloride, 168 Trimethylphosphate, 678t Trimethylsilyl capping, 600m Trimethylsilyl derivative, 565i Trimethylsilyl ester, 584m Trinitrotoluene, 443p Trioctylmethylammonium chloride, 542b Trioctylphosphine, 649i Triple point, 14t, 606b Triplet state, 404, 436, 437b Triprotic acid, 136, 194–195, 197i, 228t TRIS, 174, 179t, 222t Tris (2-aminoethyl) amine, 277p Tris(2,2Ј-bipyridine)iron, 346t Tris(2,2Ј-bipyridine)ruthenium(II), 346t, 443p Tris(hydroxymethyl)aminomethane, 174, 179t, 222t N-Tris(hydroxymethyl)methyl-2aminoethanesulfonic acid, 179t N-Tris(hydroxymethyl)methylglycine, 178t, 179t Tris(5-nitro-1,10phenanthroline)iron, 346t Tris(1,10-phenanthroline)iron, 346t Trititrotoluene, 419b Tritium, 318 Triton X-100, 540d Tropaeolin O, 221t Tryptophan, 187t TSK silica, 647t Tswett, M S., 542m t Test, 76–80, 82–83 t Test (TOST), NR2 (4.3) Tufts University, 308b Tumor cell, 384 Tungsten, 349t, 485 Tungsten carbide, 705, 707 Tungsten-hafnium separation, 542b Tungsten-halogen lamp, 447i Tungsten lamp, 447, 447i, 612 Tungsten trioxide, 493, 684 Turbidimetry, Glossary Turbidity, 689m Index Turbulent flow, 428 Two-compartment electrolysis, 371i Two one-sided t test (TOST), NR2 (4.3) Two-tailed test, 79, 80i, 82 Tylenol, 373 Type A silica, 600 Type B silica, 600 Type C silica, 600 Tyrosine, 187t, 205b Ulcer, 445b Ultra performance liquid chromatography (UPLC), 598 Ultrapure acid, 23b Ultrasonic nebulizer, 486 Ultraviolet: absorbance standard, 454t cutoff, 604t detector, 612, 612t, 661 radiation, 14, 352b, 393b, 395i vacuum, 488 Unadjusted relative retention, 545, 553 Uncertainty, 57–64, 75, App C atomic mass, 53m, 62 calibration curve, 89 confidence interval, 73 exponents, 61–62 intercept, 84, 85–87 least squares parameters, 85–87 logarithms, 61–62 molecular mass, 63 pH, 62 pipet, 63–64 principle, 488 propagation, 62t sampling, 701–705 slope, 84, 85–87 standard addition, 108 volumetric glassware, 64i x-intercept, 108 Uncle Wilbur, 415p Underpotential deposition, 369 Unified atomic mass unit, 504b Unit conversion, 15–16 Unit matrix, 423 Units of measurement, 13–16 Unmentionables, 407b Unsaturated fat, 105i Upconversion, 437b UPLC (Ultra performance liquid chromatography), 598 Uracil, 617 Uranium, 349t, 673b Urea, 140p, 226, 445b, 664, 665, 677, 678t Uric acid, 373 Urine, 24, 130i, 592p, 710, 713 Use objective, 97, 100t V (volt), 14t Vacancy, 325i Vacuum desiccator, 41i Vacuum pump, 575 Vacuum tube, 318m Vacuum ultraviolet, 488 source, 582 Validation, 100 Valine, 187t Valinomycin, 315 Valve, 6-way, 430, 431i Vanadate, 675t Vanadium(V) oxide, 707 Vanadium(V) spectrum, 420i Vanadyl sulfate, 668p van Deemter equation, 555, 575, 597 electrophoresis, 651–652 Index experimental graph, 555i, 574i, 591p, 597i, 672p mass transfer, NR17 (22.15) micellar electrokinetic chromatography, 672p Variable voltage source, 362i Variamine blue B base, 251i Varian Cary E3 spectrophotometer, 446i Variance, 69 additivity, 554, 701 analytical, 701 F test, 80–81 sampling, 701 Vasodilator, Vector, 422 Velocity, electroosmotic, 654m Ventilation blood test, 323t Vernier scale, 65p Vesicle, 13b, 27p, 384, 651 Vessel: digestion, 709–710 extraction, 711i, 712i Vibration, molecular, 405 Vibrational levels, 406 Vibrational relaxation, 406 Vibrational structure, 409, 410i Vibrational transition, 406 Vicinal silanol groups, 599i Viking Mars mission, 665m Vinegar pH, 130i Virginia Polytechnic Institute, 286d Virial coefficient, 60b Virial equation, 60b Virus, 502 Viscosity, 598, 653, 654 gas, NR18 (23.12) Visible light, 395i Vision, 456b Vitamin: biotin, 456 folic acid, 29 niacin, 671p niacinamide, 671p pyridoxal phosphate, 166 riboflavin, 413, 671p vitamin A, 341t, 456b vitamin B2, 413 vitamin B6, 166 vitamin C, 25, 107, 238b, 298t, 300i, 341t, 354, 373, 401 vitamin C formal potential, 299–300 vitamin E, 341t Void volume, 647 Vol%, 17 Volatile buffers, 519m, 614, 616 Volatile electrolyte, 679 Volcano, 460b Volhard titration, 692, 693t Volt, 14t, 281 Voltage: breakdown, 333m capillary electrophoresis, 656, 657, 657i open circuit, 364m ramp, 378 scale, 311 source, 362i unit, 14t Voltaic cell, 284 Voltammetry, 376–384 cyclic voltammetry, 382–383 microelectrodes, 383–384 polarography, 376–379 square wave, 379–380 stripping analysis, 380–382 Voltammogram, 376 Voltmeter, 287 Volume: column, 647 flow rate, 544 gravimetric analysis, 676 units, 15t Volume percent, 17 Volumetric analysis, 22 Volumetric flask, 19i, 37 Volumetric glassware uncertainty, 64i W (watt), 14t Waage, P., 118m Walden reductor, 348 Wall-coated open tubular column, 566 Warning line, 99b Washing: chromatography column, 610 storage bottle, 700t Waste: disposal, 31, 618m, NR1 (2.6) electronic, 707 reduction in HPLC, 610m remediation, 340m Wastewater, 236, 352b Watchglass, 41i Water: acid-base effect on dissociation, 165 acidity, 216b alkalinity, 216b analysis, 643i arsenic removal, 679 carbon dioxide content, 130 coordination, 142 critical constants, 606t density, 42t, 43 diffusion coefficient, 551t distillation, 700t electrolysis, 363d expansion, 42–43 hardness, 216b, 253b, 641m hydration of ions and molecules, 142b infrared absorption, 410 ion chromatography, 643i ionization, 165 irrigation, 216b, 253b isotopic molecules, 410 Karl Fischer titration, 385–386 lead, 481i metal content impurities, 540d pH, 130 “polishing”, 641 pressure of column, 670p protonated cluster, 529 purity, 605m Raman scattering, 411b refractive index, 461m resistivity, 641 softener, 641m solvation of ions, 142 temperature dependence of Kw, 129t thermal expansion, 42–43 triple point, 14t ultraviolet cutoff, 604t water of hydration, 142b Watt, 14t, 282 Waveform, 382i Waveguide, 463–465 Wavelength, 394 color, 395i selection for analysis, 400 Wavenumber, 394 WCOT, 566m Weak acid, 132–136 conjugate, 171 diprotic, 185–194 fraction of dissociation, 168, 197–198 intermediate form, 190 pH calculation, 166–170 polyprotic, 194–195 reaction with strong base, 174b titration with strong base, 208–210 titration with weak base, 226–229 Weak base, 132–136 conjugate, 171 pH calculation, 170–171 reaction with strong acid, 174b titration with weak acid, 226–229 Weak electrolyte, 16m, 167d, 168 Weakly acidic ion exchanger, 635, 636t Weakly basic ion exchanger, 635, 636t Weather Bureau, Weighing bottle, 31, 41i Weighing errors, 33–34 Weighing procedure, 31 Weight: effect of altitude, 49p tolerance of lab standards, 34t Weight percent, 17 Wenzel, T., Weston cell, 389p Wet ashing, 705, 708–710 Wet chemistry Laboratory (Mars), 308b, 323, 328, 328b Wetterhahn, K., 30m Wexler, H., Whelk-O 1, 603i Whistle noise, 473 White blood cell, 162b White chocolate, 10t White light, 457 Whitener, 407b White noise, 473 Wide-bore column, 588t Wig-L-Bug, 705 Wind power, 435b Wine, 359p, 390p Winged snail, 189b “Wired” enzyme, 374–375 Work, 14t, 281–282 Working electrode, 362, 366 potential range, 377t rotating disk, 374–376, 375i, 376i symbol, 366i Wright, W H., 318m Wt%, 17 Wulf, O., x– (mean value), 69 Xanthine, 298t Xenon lamp, 612 x-intercept uncertainty, 108 X-ray, 395i p-Xylene in iodine titrations, 353m Xylenol orange, 215i, 250, 250t, 251i, 439p y (yocto), 15t Y (yotta), 15t Yalow, R., 431m Yeast, 462 isoelectric point, 200b YO, 493i Yocto, 15t Yotta, 15t Yttrium aluminum garnet, 453i Yttrium barium copper oxide, 340b, 355b, 493i, 696p Yttrium hydroxychloride, 696p Yttrium oxide, 407b, 696p I25 z (multiple of standard deviation), 70–71 z (zepto), 15t Z (Zetta), 15t Zechmeister, L., 542m, 543i Zeeman effect, 492 Zeolite, 571i Zepto, 15t I26 Zeros, 52 Zetta, 15t Zinc: ammonia complexes, 248 EDTA titrations, 252 electrode, 312 gravimetric analysis, 675t hydroxide complexes, 139p impurity in tungsten, 485 iodimetric titration, 354t Jones reductor, 348 masking, 253 permanganate titration, 349t precipitation titration, 693t spectrophotometric analysis, 540d vapor lamp, 612 Zinc sulfate reagent, 23b Zirconia, 556i, 705 Zone broadening, electrophoresis, 656 Zooplankton, 189b Zorbax silica, 600i Zundel structure of H5Oϩ2, 127 Zwitterion, 186 bonded phase, 641 Index Periodic Table +1 20 14 Ô 0.0888 H +1 1615 454 0.53 Li Lithium † 6.941 ±2 11 1156 371 0.97 +1 Atomic Number Hydrogen 1.007 94 ±7 +2 2745 1560 1.85 Be Density at 300 K (g /cm3 ) +2 12 1363 922 1.74 1032 336 0.86 K Potassium 39.098 ±1 37 961 313 1.53 944 302 1.87 38 Rb 1650 1041 2.6 87 56 Cs 2171 1002 3.5 950 300 —– +1 Fr Francium (223) Ca 3104 1812 3.0 +2 Sr 3611 1799 4.5 Ba 3730 1193 6.7 +3 Y 89 Ra 3473 1323 10.07 Atomic mass with uncertainty in last digit Example: Ti = 47.867 ± 0.001 Numbers in parentheses are longest-lived isotope †Commercial lithium compounds are artificially depleted of Li The atomic mass of commercial Li is in the range 6.939 to 6.996 If a more accurate value is required, it must be determined for the specific material 23 3682 2175 5.8 +5,4,3,2 24 V 2945 2130 7.19 Vanadium 50.941 ±1 +4 Zr Zirconium 91.224 ±2 La Actinium (227) Ti 4682 2125 6.49 4876 2500 13.1 Ac +4,3 40 72 +3 Titanium 47.867 ±1 +3 Lanthanum 138.905 47 ±7 +2 Radium (226) Sc 3562 1943 4.50 Yttrium 88.905 85 ±2 57 Barium 137.327 ±7 1809 973 22 39 +2 88 +3 Scandium 44.955 912 ±6 Strontium 87.62 ±1 +1 Cesium 132.905 451 ±2 21 Calcium 40.078 ±4 +1 Rubidium 85.467 ±3 55 1757 1112 1.55 +2 20 Ti [Atomic masses from J Phys.Chem Ref.Data 2007, 36, 485] Na Mg +1 Common oxidation states Titanium 47.867 (Densities marked with Ô are at 273K and bar and the units are g/L) Sodium Magnesium 22.989 769 28 ±2 24.305 ±6 19 3562 1943 4.50 Melting point (K) Beryllium 9.012 182 ±3 +4,3 22 Boiling point (K) +4 Hf Hafnium 178.49 ±2 +5,3 +6,3,2 Cr Chromium 51.996 ±6 25 2335 1517 7.43 43 Nb Mo 4538 2473 11.5 42 4912 2890 10.2 Niobium Molybdenum 92.906 38 ±2 95.94 ±2 +5 74 Ta 5828 3680 19.3 73 5731 3287 16.6 Tantalum 180.947 88 ±2 +7,6,4,2,3 75 W 5869 3453 21.0 +2,3 26 3135 1809 7.86 Mn Fe +7 Tc Technetium (98) +6,5,4,3,2 Tungsten 183.84 ±1 Manganese 54.938 045 ±5 +6,5,4,3,2 41 5017 2740 8.55 +7,6,4,2,-1 Iron 55.845 ±2 44 4423 2523 12.2 27 +2,3 3201 1768 8.90 Co Cobalt 58.933 195 ±5 +2,3,4,6,8 45 +2,3,4 Ru 3970 2236 12.4 Rh Ruthenium 101.07 ±2 Rhodium 102.905 50 ±2 +2,3,4,6,8 77 +2,3,4,6 Re Os 4701 2716 22.5 Ir 76 5285 3300 22.4 Rhenium 186.207 ±1 Osmium 190.23 ±3 Iridium 192.217 ±3 104 105 106 107 108 109 —– —– —– —– —– —– —– —– —– —– —– —– —– —– —– —– —– —– Rf Rutherfordium (267) 58 3699 1071 6.78 +3,4 59 Ce 3785 1204 6.77 Cerium 140.116 ±1 90 5061 2028 11.7 Dubnium (268) +3,4 Pr Seaborgium (271) +3 60 3341 1289 7.00 91 Th —– —– 15.4 +5,4 92 Pa 4407 1405 18.9 61 Hassium (277) +3 62 +3,2 2064 1345 7.54 3785 1204 6.48 Nd Pm Sm Praseodymium Neodymium 140.907 65 ±2 144.242 ±3 +4 Bohrium (270) Promethium (145) +6,5,4,3 93 U —– 910 20.4 Protactinium Thorium Uranium 232.038 06 ±2 231.035 88 ±2 238.028 91 ±3 Samarium 150.36 ±2 +6,5,4,3 94 Np 3503 913 19.8 Neptunium (237) +6,5,4,3 Plutonium (244) Meitnerium (276) 63 +3,2 1870 1090 5.26 Eu Europium 151.964 ±1 95 2880 1268 13.6 +6,5,4,3 Am Americium (243) 18 of the Elements 13 14 +3 4275 2300 2.34 4470 4100 2.62 B Boron 10.811 ±7 2793 933 2.70 10 11 +2,3 28 3187 1726 8.90 Ni Nickel 58.693 ±2 46 3237 1825 12.0 Pd 2436 1234 10.5 Pt Platinum 195.084 ±9 30 Cu 1180 693 7.14 +1 48 Ag 1040 594 8.65 Silver 107.868 ±2 79 3130 1338 19.3 +3,1 Au Gold 196.966 569 ±4 Ds —– —– —– +2 31 Zn 2478 303 5.91 +2 49 Cd 2346 430 7.31 630 234 13.5 81 Hg 1746 577 11.85 Mercury 200.59 ±2 3540 1685 2.33 Si Silicon 28.085 ±3 32 Ga 3107 1210 5.32 +4 Ge Germanium 72.64 ±1 +3 In Indium 114.818 ±3 +2,1 +4 14 +3 Gallium 69.723 ±1 Cadmium 112.411 ±8 80 Al Aluminum 26.981 538 ±8 Zinc 65.409 ±4 111 110 —– —– —– +2,1 Copper 63.546 ±3 47 +2,4 4100 2045 21.4 2836 1358 8.96 +2,4 Palladium 106.42 ±1 78 29 12 C Carbon 12.010 ±8 +3 13 +3,1 Tl Thallium 204.383 ±2 50 2876 505 7.30 2023 601 11.4 77 63 1.234 Ô 550 317 1.82 Phosphorus 30.973 762 3,5 33 876 —– 5.72 As Arsenic 74.921 60 ±2 51 Sn 1860 904 6.68 83 Pb 1837 545 9.8 718 388 2.07 -2,4,6 34 958 494 4.80 Se Selenium 78.96 ±3 Sb Bismuth 208.980 40 ±1 S Sulfur 32.065 ±5 1261 723 6.24 Bi ±2,4,6 16 52 +3,5 O Helium 4.002 602 -1 85 53 Ô 1.674 F -2,4,6 Te Tellurium 127.60 ±3 +4,2 84 1235 527 9.4 Po Polonium (209) 17 +3 3539 1585 7.89 Gd Gadolinium 157.25 +3 239 172 Ô 3.12 Cl 87 84 ¤ 1.760 Chlorine 35.453 ±2 3496 1630 8.27 66 Tb 2835 1682 8.54 67 Dy 2968 1743 8.80 +3 68 Ho 3136 1795 9.05 Terbium Dysprosium Holmium 158.925 35 ±2 162.500 ±1 164.930 32 ±2 98 Cm Bk —– 900 —– Curium (247) +3 97 —– —– —– Berkelium (247) +3 Cf Californium (251) 99 —– —– —– +3 69 Er 2220 1818 9.33 Erbium 167.259 ±3 100 —– —– —– +3,2 Tm Thulium 168.934 21 ±2 35 332 266 3.12 1,5 36 Br 120 116 Ô 3.69 Bromine 79.904 ±1 53 458 387 4.92 85 610 575 —– Einsteinium (252) Fermium (257) 70 1467 1097 6.98 ±1,5,7 I 86 At 211 202 Ô 9.78 +3 Yb 3668 1936 9.84 Lu Lutetium 174.967 ±1 103 —– —– —– —– —– —– Mendelevium (260) No Nobelium (259) Rn Radon (222) 71 102 Xe Xenon 131.293 ±6 ±1,3,5,7 Astatine (210) —– —– Kr 54 165 161 Ô 5.78 +3,2 Ytterbium 173.04 ±3 Ar Krypton 83.798 ±2 Iodine 126.904 47 ±3 101 Es Fm Md Ne Argon 39.948 ±1 Rg +3,4 27 25 Ô 0.889 18 112 +4,3 96 1340 13.5 65 10 ±1,3,5,7 Darmstadtium Roentgenium (281) (280) 64 He Oxygen Fluorine Neon 15.999 ±3 18.998 403 ±5 20.179 ±6 ±3,5 Antimony 121.760 ±1 +4,2 Lead 207.2 ±1 N 90 50 Ô 1.410 P 17 -2 3,5,4 15 16 ±3,5,4,2 Nitrogen 14.006 ±2 +4,2 Tin 118.710 82 4.2 0.95 Ô 0.176 15 4,2 Lr Lawrencium (262) Physical Constants (2006) Term Symbol Value Elementary charge e Speed of light in vacuum c Planck’s constant h h/2␲ h Avogadro’s number Gas constant N R Faraday constant (ϭ Ne) Boltzmann’s constant (ϭ R/N) F k Electron rest mass me Proton rest mass mp Dielectric constant (permittivity) of free space Gravitational constant ␧0 G 1.602 176 487 (40)† ϫ 10Ϫ19 C 4.803 204 27 (12) ϫ 10Ϫ10 esu 2.997 924 58 ϫ 108 m/s ϫ 1010 cm/s 6.626 068 96 (33) ϫ 10Ϫ34 J ؒ s ϫ 10Ϫ27 erg ؒ s 1.054 571 628 (53) ϫ 10Ϫ34 J ؒ s ϫ 10Ϫ27 erg ؒ s 6.022 141 79 (30) ϫ 1023 molϪ1 8.314 472 (15) J/(mol ؒ K) V ؒ C/(mol ؒ K) ϫ 10Ϫ2 L ؒ bar/(mol ؒ K) ϫ 107 erg/(mol ؒ K) 8.205 746 (15) ϫ 10Ϫ5 m3 ؒ atm/(mol ؒ K) ϫ 10Ϫ2 L ؒ atm/(mol ؒ K) 1.987 207 (4) cal/(mol ؒ K) 9.648 533 99 (24) ϫ 104 C/mol 1.380 650 (24) ϫ 10Ϫ23 J/K ϫ 10Ϫ16 erg/K 9.109 382 15 (45) ϫ 10Ϫ31 kg ϫ 10Ϫ28 g 1.672 621 637 (83) ϫ 10Ϫ27 kg ϫ 10Ϫ24 g 8.854 187 817 ϫ 10Ϫ12 C2/(N ؒ m2) 6.674 28 (67) ϫ 10Ϫ11 m3/(s2 ؒ kg) † Numbers in parentheses are the one-standard-deviation uncertainties in the last digits P J Mohr, B N Taylor, and D B Newall, 2006 CODATA Values, from http://physics.nist.gov/constants (August 2007) SOURCE: Concentrated Acids and Bases Name Acid Acetic Hydrochloric Hydrofluoric Nitric Perchloric Phosphoric Sulfuric Base Ammonia† Sodium hydroxide Potassium hydroxide † Approximate weight percent Molecular mass Approximate molarity Approximate density (g/mL) mL of reagent needed to prepare L of ϳ1.0 M solution 99.8 37.2 49.0 70.4 70.5 85.5 96.0 60.05 36.46 20.01 63.01 100.46 97.99 98.08 17.4 12.1 31.8 15.8 11.7 14.7 18.0 1.05 1.19 1.30 1.41 1.67 1.69 1.84 57.3 82.4 31.4 63.5 85.3 67.8 55.5 28.0 50.5 45.0 17.03 40.00 56.11 14.8 19.3 11.5 0.90 1.53 1.44 67.6 51.8 86.6 28.0 wt% ammonia is the same as 56.6 wt% ammonium hydroxide Titration of weak acid HA with strong base OH− 12 HA + OH− → A− + H2O Equivalence point A− + H2O HA + OH− F′ − x x x x2 = Kb F′ − x 10 Excess OH− Kw [OH−] pH = − log pH Buffer region [A−] pH = pKa + log [HA] Initial point HA H+ + A− F−x x x x2 = Ka F−x 10 20 30 40 50 60 Volume of base added (V b ) 11 Titration of weak base B with strong acid H+ B + H+ → BH+ Initial point B + H2O BH+ + OH− x x F−x x2 = Kb F−x pH Excess H+ Buffer region [B] pH = pKa + log [BH+] pH = − log [H+] Equivalence point BH+ B + H+ F′ −x x x x2 = Ka F′ − x 10 20 30 Volume of acid added (V a ) 40 50 60 ... Microsoft By changing cell: C4 D4 = C4 ^3/(2+A6 *C4 ) Excel are described as they are needed These 10 C7 = A4 /C4 ^2 OK Cancel features include graphing in Chapters and 4, 11 D8 = A6 *C7 *C4 statistical... in California’s Sierra Nevada In addition to its high energy content, chocolate packs an extra punch with the stimulant caffeine and its biochemical precursor, theobromine O C HN C C C H 3C N CH3... CO2 xiii Chemical Measurements Biochemical Measurements with a Nanoelectrode 1-1 1-2 1-3 1-4 SI Units Chemical Concentrations Preparing Solutions Stoichiometry Calculations for Gravimetric Analysis