Quantitative chemical analysis daniel c harris 7th edition

www.elsolucionario.org Quantitative Chemical Analysis [“The Experiment” by Sempe © C Charillon, Paris.] www.elsolucionario.org Quantitative Chemical Analysis SEVENTH EDITION Daniel C Harris Michelson Laboratory China Lake, California W H Freeman and Company New York Publisher: Craig Bleyer Senior Acquisitions Editor: Jessica Fiorillo Marketing Manager: Anthony Palmiotto Media Editor: Victoria Anderson Associate Editor: Amy Thorne Photo Editors: Cecilia Varas/Donna Ranieri Design Manager: Diana Blume Cover Designer: Trina Donini Text Designer: Rae Grant Text Layout: Jerry Wilke Senior Project Editor: Mary Louise Byrd Illustrations: Fine Line Illustrations Illustration Coordinators: Shawn Churchman/Susan Timmins Production Coordinator: Paul W Rohloff Composition: TechBooks/GTS Companies, York, PA Printing and Binding: RR Donnelley Library of Congress Control Number: 2006922923 ISBN: 0-7167-7041-5 EAN: 9780716770411 © 2007 by W H Freeman and Company Printed in the United States of America First printing Brief Contents The Analytical Process 17 Electroanalytical Techniques 348 Measurements 18 Fundamentals Tools of the Trade 20 Experimental Error 39 Statistics 53 Quality Assurance and Calibration Methods 78 Chemical Equilibrium 96 Let the Titrations Begin 121 Activity and the Systematic Treatment of Equilibrium 140 10 Polyprotic Acid-Base Equilibria 180 199 12 EDTA Titrations 228 13 Advanced Topics in 250 14 Fundamentals of Electrochemistry 402 20 Spectrophotometers 424 21 Atomic Spectroscopy 453 22 Mass Spectrometry 474 23 Introduction to Analytical Separations 501 528 25 High-Performance Liquid 556 26 Chromatographic Methods and Capillary Electrophoresis 588 11 Acid-Base Titrations Equilibrium of Spectrophotometry Chromatography 158 378 19 Applications 24 Gas Chromatography Monoprotic Acid-Base Equilibria of Spectrophotometry 270 27 Gravimetric and Combustion Analysis 28 Sample Preparation Notes and References NR1 Glossary GL1 Appendixes AP1 Solutions to Exercises S1 15 Electrodes and Potentiometry 298 Answers to Problems AN1 16 Redox Titrations Index I1 327 628 644 www.elsolucionario.org This page intentionally left blank Contents Preface The Analytical Process A Biosensor for Arsenic in the Environment 0-1 The Analytical Chemist’s Job 0-2 General Steps in a Chemical Analysis Box 0-1 Constructing a Representative Sample Measurements 1-1 1-2 1-3 1-4 Ultrasensitive Measurement of Atoms in a Vapor SI Units Chemical Concentrations Preparing Solutions Stoichiometry Calculations Tools of the Trade The Smallest Balances 2-1 Safe, Ethical Handling of Chemicals and Waste Box 2-1 Disposal of Chemical 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 Experimental Error Experimental Error 3-1 Significant Figures 3-2 Significant Figures in Arithmetic 3-3 Types of Error Box 3-1 Standard Reference Materials 3-4 Propagation of Uncertainty from Random Error Box 3-2 Propagation of Uncertainty in the Product x и x 3-5 Propagation of Uncertainty: Systematic Error Statistics Is My Red Blood Cell Count High Today? 4-1 Gaussian Distribution xiii 7 9 12 14 16 20 20 21 22 22 25 26 27 29 30 31 33 35 39 39 40 42 43 44 48 49 53 53 4-2 Confidence Intervals 57 4-3 Comparison of Means with Student’s t 59 Box 4-1 Analytical Chemistry and the Law 63 4-4 Comparison of Standard Deviations with the F Test 63 4-5 t Tests with a Spreadsheet 64 4-6 Q Test for Bad Data 65 4-7 The Method of Least Squares 65 4-8 Calibration Curves 69 Box 4-2 Using a Nonlinear Calibration Curve 71 4-9 A Spreadsheet for Least Squares 71 Quality Assurance and Calibration Methods The Need for Quality Assurance 5-1 Basics of Quality Assurance Box 5-1 Control Charts 5-2 Method Validation Box 5-2 The Horwitz Trumpet: Variation in Interlaboratory Precision 5-3 Standard Addition 5-4 Internal Standards 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 6-8 Solving Equilibrium Problems with a Concentration Table and a Spreadsheet Let the Titrations Begin Evolution of the Buret 7-1 Titrations 78 79 81 82 85 87 90 96 97 98 100 101 102 102 104 105 107 108 109 110 113 114 121 121 vii 7-2 7-3 7-4 7-5 7-6 7-7 7-8 Box 7-1 Reagent Chemicals and Primary Standards Titration Calculations Spectrophotometric Titrations The Precipitation Titration Curve Titration of a Mixture Calculating Titration Curves with a Spreadsheet End-Point Detection Demonstration 7-1 Fajans Titration Efficiency in Experimental Design 123 123 126 127 131 132 133 134 134 Activity and the Systematic Treatment of Equilibrium 140 Hydrated Ions 8-1 The Effect of Ionic Strength on Solubility of Salts Demonstration 8-1 Effect of Ionic Strength on Ion Dissociation Box 8-1 Salts with Ions of Charge Ն|2| Do Not Fully Dissociate 8-2 Activity Coefficients 8-3 pH Revisited 8-4 Systematic Treatment of Equilibrium Box 8-2 Calcium Carbonate Mass Balance in Rivers 8-5 Applying the Systematic Treatment of Equilibrium 141 143 143 147 147 150 150 9-1 9-2 9-3 9-4 9-5 159 159 161 162 viii 11-1 11-2 11-3 11-4 11-5 11-6 11-7 11-8 11-9 199 Acid-Base Titration of a Protein 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 Box 11-1 Alkalinity and Acidity Finding the End Point with Indicators Demonstration 11-1 Indicators and the Acidity of CO2 Box 11-2 What Does a Negative pH Mean? Box 11-3 World Record Small Titration Practical Notes The Leveling Effect Calculating Titration Curves with Spreadsheets 12 EDTA Titrations 200 202 205 206 208 209 212 214 214 216 216 216 218 228 Ion Channels in Cell Membranes 12-1 Metal-Chelate Complexes 12-2 EDTA Box 12-1 Chelation Therapy and Thalassemia 12-3 EDTA Titration Curves 12-4 Do It with a Spreadsheet 12-5 Auxiliary Complexing Agents Box 12-2 Metal Ion Hydrolysis Decreases the Effective Formation Constant for EDTA Complexes 12-6 Metal Ion Indicators Demonstration 12-1 Metal Ion Indicator Color Changes 12-7 EDTA Titration Techniques Box 12-3 Water Hardness 229 231 232 235 237 238 240 241 241 244 245 164 165 166 167 170 171 10 Polyprotic Acid-Base Equilibria 180 Proteins Are Polyprotic Acids and Bases 10-1 Diprotic Acids and Bases Box 10-1 Successive Approximations 10-2 Diprotic Buffers 10-3 Polyprotic Acids and Bases 190 191 193 194 11 Acid-Base Titrations 141 Monoprotic Acid-Base Equilibria 158 Measuring pH Inside Cellular Compartments Strong Acids and Bases Box 9-1 Concentrated HNO3 Is Only Slightly Dissociated Weak Acids and Bases Weak-Acid Equilibria Box 9-2 Dyeing Fabrics and the Fraction of Dissociation Demonstration 9-1 Conductivity of Weak Electrolytes Weak-Base Equilibria Buffers Box 9-3 Strong Plus Weak Reacts Completely Demonstration 9-2 How Buffers Work 10-4 Which Is the Principal Species? 10-5 Fractional Composition Equations 10-6 Isoelectric and Isoionic pH Box 10-2 Isoelectric Focusing 181 186 187 188 13 Advanced Topics in Equilibrium 250 13-1 13-2 13-3 13-4 Acid Rain General Approach to Acid-Base Systems Activity Coefficients Dependence of Solubility on pH Analyzing Acid-Base Titrations with Difference Plots 251 254 257 263 14 Fundamentals of Electrochemistry 270 Electricity from the Ocean Floor 14-1 Basic Concepts 270 Contents www.elsolucionario.org Hypophosphorous acid, 328t Hypoxanthine, 289t Hz (hertz), 10t Ipa, 368i Ipc, 368i Ibuprofen, 499p Ice core, 395b ICP, 461t Ideal gas law, 18p Ignition, 30, 634 Imazaquin, 490i, 492 Imidazole, 370 Imidazole hydrochloride, 175t Iminodiacetic acid, 246p, 594m Immiscible liquids, 502m Immobilized pH gradient, 194b Immunoassay, 411–412 Immunoglobulin, 413, 602 Imperial College, 628 Implant, 501 “Implies that” symbol, 15m Imprinted polymer, 441, 442i, 603b Impurities in reagents, 123b in (inch), 11t Inclusion, 633 Independent equations, 251m Indeterminate error, 43 Index of refraction, 452p India rubber, 121 Indicator, 122 acid-base, 212–216, 214d, 215t adsorption, 133, 134d electrode, 299, 301–302, 302d, 329 error, 213, 223p metal ion, 241–243, 241d, 242t precipitation, 133, 134t redox, 333t, 338 solution preparation, 215t Indigo tetrasulfonate, 333t Indirect detection, 598, 614, 615i Indirect titration, 244–245, 339 Individual hardness, 245b Induction coil, 460 Inductively coupled plasma, 460–461, 463–464, 468 mass spectrometry, NR13 (21.17) Inductively coupled plasma/mass spectrometry, 313, 453, 468–470 Inert electrode, 272 Inert salt, 141 Inflection point, 129, 200i, 201, 204i Infrared cutoff, 384m Infrared detector, 437, 543t, 571t, 638 Infrared radiation, 380i Infrared window, 384m Injection: capillary electrophoresis, 611–612 gas chromatography, 538–541, 551 graphite furnace, 457i HPLC, 571 precision, 84 variance (chromatography), 517 valve, 571 Inorganic carbon, 338b Inorganic ion exchanger, 593 Inorganic material, dissolution, 652–654 In situ, 357m Instrument detection limit, 87 Instrument noise, 385 Instrument precision, 84 Insulator, 318 Insulin, 562i Integration (peak area), 541–542 Intensity (irradiance), 381m Intercalation, 413 Index Intercept, 66–67 INTERCEPT (Excel), 69 Interconversion, salt, 594 Interdigitated electrodes, 360b Interference: atomic spectroscopy, 466–468 chemical, 8m, 387 filter, 433 fringes, 450p gravimetric analysis, 630t ion-selective electrodes, 312, 314t isobaric, 469 light rays, 430i noise, 449 Interferogram, 444i, 445 Interferometer, 443i Interferometry, 443–445 Interlaboratory precision, 84, 85b Intermediate form of diprotic acid, 184 Intermediate precision, 84 Internal conversion, 390 Internal standard, 90–91, 542 Interpolation, 40m, 145 Interpretation of results, Intersystem crossing, 390 Intestine, 167i Intra-assay precision, 84 Intracellular O2, 416–417 Intracellular pH, 158 Inulin, 506m Inverse matrix, 406 Inversion, population, 428 In vivo microdialysis, 556 Iodate, 21b, 94p, 130, 328t, 340m, 343t, 500p Iodide: complexes, 103–104, 119p diffusion coefficient, 513t electrolysis, 350d gravimetric analysis, 630t ion-selective electrode, 314t, 316m, NR7 (15.6) precipitation titration, 134t stripping analysis, 366t Iodimetry, 340, 341t, 371d Iodine: isotope abundance, 479t Karl Fischer titration, 371, 371d oxidant, 328t redox potentials, 282b redox titrations, 340–343, 341t, 343t refractive index, 438m standardization, 340 starch indicator, 334–335, 340 Iodometry, 340, 343t superconductor analysis, 327, 342b, 347p Ion: diffusion coefficient, 513t hydration, 140 size, 144t, 145 snow composition, 594m solvation, 140 Ion chromatography, 594–597, NR16 (26.5) Ion exchange bead, 644 enantiomer separation, 594 equilibrium, 307 glass surface, 307 liquid ion exchanger, 314–316 preconcentration, 659t reference electrode drift, 311i water purification, 594 Ion-exchange chromatography, 507i, 508, 566i, 589–594 applications, 594 deionization, 594 Donnan equilibrium, 592 functional groups, 589, 590t, 591t gels, 590m, 591t, 593 gradient elution, 593, 593i interconversion of salts, 594 ion chromatography, 594–597 ion exchangers, 589–591, 591t, 593 ion-exclusion, 593 ion-pair chromatography, 598–599 preconcentration, 594 resins, 589, 590m, 592t, 593 salt interconversion, 594 selectivity, 590t, 591, 592t sugar separation, 348 Ion exchanger: drug stabilization, 594 drug tablets, 594 Ion-exclusion chromatography, 593 Ionic atmosphere, 141, 632m, 633 Ionic liquid, NR15 (24.8) Ionic radius, 140 Ionic strength effects: activity coefficient, 145, 146i buffer pKa effect, 174f ion dissociation, 141d molecular exclusion, 601 pH, 147 solubility, 141–142 Ionization: energy, 468, 476, 477i interference, 467 mass spectrometry, 475–477 suppressor, 467 Ion mobility, 303t Ion mobility spectrometer, 487–488, 627p Ionophore, 304, 313 Ion pair, 100–101, 110b, 142, 143b, 146m, 165f, 218, 253–254, 257, App J Ion pore, 228 Ion-selective electrode, 303–318 advantages, 317 bromide, 314t cadmium, 316m calcium, 314–315, 316m chloride, 314t compound, 316 cyanide, 314t detection limit, 316 fluoride, 313–314, 314t gas-sensing, 317 halide, 314t heparin, 298, 315 history, NR7 (15.7) hydrazoic acid, 317 iodide, 314t, 316m, NR7 (15.6) lead, 313, 316 leakage, 316 liquid-based, 314–316 mechanism, 303–306 mercury, 325–326p operating tips, 317 perchorate, 316m potassium, 316m relative error, 317m selectivity coefficient, 312 silver, 316m sodium, 316m solid-state, 313–315, 316m, 318–321 standard addition, 317 sulfide, 314t thiocyanate, 314t Ion source, 475i Ion spray, 488 Ion-trap spectrometer, 486 Iridium, 651 pH electrode, NR7 (15.14) Iron: blood, 385–387 colloid, 630i deposition on electrode, 369i, 370 DTPA complex, 231i EDTA complex, 234i ferrozine complex, 386i glycine equilibria, 268p gravimetric analysis, 16, 630t, 631 hollow-cathode spectrum, 455i hydrolysis, 632d isotope abundance, 479t Jones reductor, 336 masking, 245, 245b nitrilotriacetate complex, 231i overload, 232b permanganate standardization, 337 permanganate titration, 337t rainwater, 385m reaction with thiocyanate, 141 redox titration, 327–332, 332d serum iron determination, 385–387 spectrophotometric titration, 126 standard, 337 transferrin complex, 126 transferrin reduction, 291 waste remediation, 327m Iron(II), electron transfer, 328b Iron(III): hydroxide, 634 ocean floor, 270 oxide, 16, 30 stripping analysis, 366–367 thiocyanate, 133, 141, 267p, 421p Iron(VI), 327m, 328t Irradiance, 381, 424 Irrigation water, 209b, 245b Isobaric interference, 469 Isobutane, chemical ionization, 477 Isobutyl groups on silica, 561i Isocratic elution, 564i, 565, 576–577, 582 Isoelectric focusing, 194b Isoelectric point (pH), 193, 194b, 199i Isoionic point (pH), 193, 199 Isoleucine, 182t Isosbestic point, 406, 419p Isotherm, 521 Isotope: abundance, 479t, 480t dilution, 500p discovery, 474m distribution, 555p lead, 475i mass, 479t measurement, 394, 395b patterns, 479–481, 480t, 496p, 499p ratio, 395b, 424, 474, 528 separation, 515i, 615i table, 479t Isotope ratio mass spectrometry, 482b Iteration (Excel), 156p J (joule), 10t Jellyfish, 397 Jet Propulsion Laboratory, 11m Job’s method, 408 Jones reductor, 336, 655 Jorgensen, J W., 604m Joule, 10, 10t, 11m, 272 Joule heating, 607 Junction, pn, 319 Junction potential, 303, 310b, 311, 324p free diffusion junction, NR7 (15.20) I11 K (kelvin), 9t k* (average capacity factor), 582b k (kilo), 10t Ka (acid dissociation constant), 110, 112–114 Kb (base hydrolysis constant), 110, 112–114 Kw, 107, NR6 (13.10) Kaolinite, 260 Karl Fischer jacks of pH meter, 371d Karl Fischer titration, 370–372 Kelvin, 9t Ketone, 338, 659 kg (kilogram), 9t KHP (potassium hydrogen phthalate), 185, 217t Kidney dialysis, 632d Kilo, 10t Kilogram, 9t Kimax, 26m Kinetic energy, 476b, 485m Kinetic prediction, 100 Kjeldahl flask, 125, 125i Kjeldahl nitrogen analysis, 124–125, 339b digestion, 654 functional groups, NR4 (7.4) iodometric titration, 346p titration, 225p Klemensiewicz, 306m Knife edge, 23 Kohlrausch, F., 108 Kovats index, 535, 537t L (liter), 11t, 12 ␭ (wavelength), 379 Label, chemical hazard, 21i Lab-on-a-chip, 620–622 Laboratory coat, 21 Laboratory notebook, 22 Laboratory sample, 645, 650 Lactalbumin, 494b, 619i, 626p Lactate, 289t, 312t Lactate dehydrogenase, 601i Lactic acid, 257m Lactoglobulin, 194b, 494b Lactose, 348, 614i lacZ, Lake water, 261i Lamp, 426–427 deuterium, 571 fluorescent, 391b quartz-halogen, 425 Lanthanide elements, 144f extraction, 656m separation, 593i Lanthanum: permanganate titration, 337t precipitation titration, 157p releasing agent, 467 Lanthanum fluoride, 157p, 313, 314t Lanthanum phosphate, 643p Lanthanum-sulfate equilibria, 257p Laser, 424, 427–428, 455i ablation, 453, 470, NR13 (21.1) crystal, 327, 345p desorption, 494b diode, 428 Latimer diagram, 282b Law, 63b Law of mass action, 97, 143 lb (pound), 11t Lead: analysis, 660p atomic fluorescence, 455i carbonate, 455i coprecipitation, 660p disposal, 21b I12 dust, 18p EDTA titration, 244, 245 flame photometric detector, 549 gravimetric analysis, 630t iodide complexes, 103–104 iodimetric titration, 341t ion-selective electrode, 313, 314, 316 isotopes, 475i, 479t masking, 245 metal ion buffer, 316 permanganate titration, 337t remediation with plants, 244m spectrophotometric analysis, 504d trace analysis, 78, 645 uranium decay, 628 Lead(II) iodide, 101i Lead(IV) acetate, 328t Lead silicate, 21b Lean flame, 457 Least squares: error analysis, 67–69 intercept, 67–68 linear, 65–69 nonlinear, NR2 (4.6) slope, 67–68 spreadsheet, 71–72 standard addition, 90 Le Châtelier’s principle, 99–100, 141d, 168, 250, 467m Lemon pH, 108i Length, 9t, 11t Leucine, 181–185, 182t Leucosafranine, 289t Leveling effect, 216 Levitation, 327 Lewis acid, 103, 229 Lewis base, 103, 229 Library (mass spectra), 476 Lifetime, fluorescence, 391, 412 Ligand, 102, 229 Light: absorbance, 381, 382b absorption, 380–383 absorption spectrum, 383d Beer’s law, 381, 382b, 402 blackbody radiation, 426b, 427 coherence, 428 collimation, 428m, 429 color, 380i, 382, 383t complementary color, 382, 383t diffraction, 429 Doppler effect, 463 effect on silver, 134 electric field, 379 electromagnetic spectrum, 380, 380i, 383d emission, 391b, 392–397, 455i fluorescence, 383d, 390–391, 392–397 frequency, 379, 380i gamma ray, 380i infrared, 380i interference, 430i luminescence, 392–397 magnetic field, 379 microwave, 380i phosphorescence, 390–391 plane-polarized, 379 polarization, 428 properties, 379–380 quantitative analysis, 385–387, 402–406 radio wave, 380i refraction, 437–438 refractive index, 379, 437 sources, 426–428 spectrophotometer, 394i, 424–437, 425i spectrum, 380i speed, 9t, 379, 443m stray, 432 time-resolved fluorescence, 412 transmittance, 381–383 ultraviolet, 378, 380i visible, 380i wavelength, 379, 380i wavenumber, 379 white, 435 X-ray, 380i Light bulb, 54, 391b Light scattering detector, 573–574 Light stick, 397 Light switch, 413 Limestone, 137p, 250 Limit of detection, 84–87 Lincomycin, 371 Line (graph), App B Linear calibration curve, 69–71 Linear equations, 405–406 Linear flow rate, 508, 558 Linear interpolation, 145 Linearity, 83 Linear range, 71, 468, 543t, 572m Linear regression, 65–69 Linear response, 70 Line noise, 449 Line notation, 277 LINEST (Excel), 68–69, 83, 135 multiple regression, 135 Linewidth, atomic spectroscopy, 454, 455i, 462–463 Lipophilicity, 199 Liquid, standard state, 97 Liquid-based ion-selective electrode, 303, 314–316 Liquid chromatography: additives, 568 affinity chromatography, 602–603 bandshape, 569–570 bonded phase selection, 579–580, 579t buffer, 576t chiral separation, 561i, 569b column, 566–567, 568, 576t dead volume, 570 detection limit, 571t detector, 571–575 dwell time, 581 dwell volume, 581 electrochemical detector, 348 eluent strength, 569, 579i equipment, 557i flow rate, 576t gradient elution, 580–583 HPLC, 556–583 injection, 571, 571i ion chromatography, 594–597 ion exchange, 589–594 isocratic elution, 576–577, 582 method development, 575–583 mobile phase, 576t molecular exclusion, 599–602 particle-size effect, 557–558, 559t peak asymmetry, 576 preparative, 569b pressure, 558, 576 1-propanol in solvent, 568 resolution, 579m rule of three, 577m sample size, 576t scaling gradient, 582b selecting mode, 566–567 silica, 559i, 560i solvent additive, 568 solvent use, 568 starting conditions, 576t stationary phase, 559–562, 576t tailing, 560i, 569 temperature, 576t, 579 theoretical plates, 558, 559t Liquid chromatography/mass spectrometry, 488–495 Liquid junction, 310b Liquid-liquid extraction, 656–657 Liter, 11t, 12 Lithium: diffusion coefficient, 513t isotopes, 75p solvation, 140 Lithium battery, 346p Lithium borate, flux, 653, 653t Lithium cobalt oxide, 346p Lithium fluoride: ion pair, 156p solubility, 156p Lithium hydroxide, 108t, 119p Litmus, 215t Lobster, 229m Logarithm, App A significant figures, 41–42, 128 uncertainty, 47–48 Longitudinal diffusion, 518, 609 Longitudinal heating, 458 Loop, sample, 571 Lord Rayleigh, 60 Lot, 645 Lower limit of detection, 84 Lower limit of quantitation, 86 Luggin capillary, 353i Luminescence: absorption and emission, 392–397 analytical applications, 416–417, 423p intensity, 395–396, 397i lifetime, 412 quenching, 414–416, 423p sensor, 416, 439 Luminol, 397 Luminous intensity, 9t Lutetium-177, 230 Lutidine buffers, 174f L’vov platform, 458i Lye pH, 108i Lysine, 182t, 608 Lysosome, 158 Lysozyme, 562i m (meter), 9t m (milli), 10t m (molality), 12 M (mega), 10t M (molarity), 12 ␮ (ionic strength), 142 ␮ (mean), 54 ␮ (micro), 10t MacKinnon, R., 228 Macrophage, 158 Magnesium: EDTA titration, 241d, 245 electrolyte balance, 312t gravimetric analysis, 630t, 634, 636 ocean, 12 permanganate titration, 337t water hardness, 245b Magnesium chloride, 12 ion pair, 143b Magnesium hydroxide, 109t solubility, 153–154 Magnesium nitrate, 460 Magnesium oxide, 460 Magnesium perchlorate, 31t, 637i Magnesium pyrophosphate, 635 Index Magnesium sulfate ion pair, 142, 143b Magnetic field, mass spectrometry, 476b Magnetic force, 476b Magnetic levitation, 327 Magnetic sector mass spectrometer, 475, 476b Magnetic stirring, 122i Makeup gas, 538, 543 Malate, 289t MALDI, 494b Maleate, 626p Malic acid, 186b Malonate, 120p Malonic acid, 136p, 302d, 338 Maltose, 348 Manganate, 336 Manganese: atomic absorption, 459i EDTA complex, 229i emission, 391b gravimetric analysis, 630t masking, 245 serum, 645t Manganese(III), 357 Manganese dioxide, 336, 343t Manganese hydroxide, solubility, 155p Manganous ion, 336 Man-in-vat problem, 643p Mantissa, 42 Marble, 250, 260 Marble table, 23 Marine diet, 528 Mars Climate Orbiter, 11m Martin, A J P., 508m, 514m Masking, 8m, 245b, 387, 634 Mass: atomic, 476b balance, 132, 148, 191 equivalent, App E isotopes, 479t molecular, 476b nominal, 476b single cell, 474 units, 9t, 11t Mass action law (equilibrium constant), 97, 143 Mass spectrometer: atmospheric pressure chemical ionization, 490–491 calibration, 481 detector, 571t double focusing, 484 electrospray, 488–490 gas chromatography, 537 high-resolution, 484 ion spray, 488 magnetic sector, 475, 476b MALDI, 494b MS/MS, 492i, 492m resolving power, 484, 486 tandem, 492i, 492m time-of-flight, 485–486 triple quadrupole, 492i Mass spectrometry, 453, 474–495, NR13 (22.5) atmospheric pressure chemical ionization, 490–491 calibration, 481 capillary electrophoresis, 490, 490i charge reduction, NR14 (22.22) chemical ionization, 477 chromatography, 488–495, 541, 543t collisionally activated dissociation, 490, 493 double focusing, 481, 484 electron ionization, 475 Index electrophoresis/mass spectrometry, 490, 490i electrospray, 488–490, 493 fragmentation pattern, 483–484 high-resolution, 481, 481i, 484 inductively coupled plasma, 453, 468–470 ion spray, 488 ion-trap, 486 isotope dilution, 500p isotope patterns, 479–481, 496p, 499p isotope ratio, 482b, 528 magnetic sector, 475 MALDI, 494b mass spectrum, 474, 477, 478–484 matrix-assisted laser desorption/ionization, 494b molecular ion, 478–483 MS/MS, 492m nominal mass, 476b proteins, 493–495, 494b quadrupole ion-trap, 486 quadrupole transmission, 484 resolving power, 478, 484, 486 selected ion monitoring, 491–492 selected reaction monitoring, 491–493 spectral interpretation, 478–484 tandem, 492m time-of-flight, 485–486 transmission quadrupole, 484 Mass spectrometry/mass spectrometry, 492m Mass spectrum, 474, 477, 478–484 data base, NR14 (22.8) library, 476 Mass titration, 26 Mass transfer, 519, 538, 562 Mast cell, 298 Material balance, 148 Material Safety Data Sheet, 22 Matrix, 80, 87, 317, 459, 494b effect, 87 modifier, 459 Matrix (mathematics), 406 Excel, 68–69 multiplication, NR11 (19.3) Matrix-assisted laser desorption/ ionization, 494b Matrix-matched standard, 470, App K Mauna Loa, 427b McLafferty rearrangement, 483i Mean, 54 comparison, 59–62, 64–65 Mean free path, 499p Measuring pipet, 27 Meat nitrogen content, 125t Mechanical balance, 23 Mechanism of electron transfer, 328b Mediator, 360 Mega, 10t Meissner effect, 327 Membrane: cell, 228 extraction, 644 glass, 306–307 semipermeable, 316, 556, 632d Memory effect, 458 Meniscus, 25, 27i 2-Mercaptoethanol, 120p, 341t, 619 Mercuric chloride, 651 Mercurous ion, 100m Mercury: amalgam, 456b battery, 292p cleanup, NR10 (17.15) coffee bean, 468, 469i cold vapor atomic fluorescence, 456b density, 33m EDTA titration, 244 EDTA titration electrode, 235i, 322p electrode, 302, 362–363, 574 emission, 391b global distribution, 456b gold absorption, 456b iodimetric titration, 341t ion-selective electrode, 325–326p isotope abundance, 479t lamp, 571 masking, 245 metal ion buffer, 325–326p poisoning, 21m potential range, 363m spectrophotometric analysis, 504d trace analysis, 645 Mercury cadmium telluride, 437 Mercury(I), 100m, 134t disproportionation, 100m, 101b hydrolysis, 101b Mercury(I) chloride, 300 Mercury(II) acetate, 356i Mercury(II) iodate, 335 Mercury(II) oxide, 217t MES (2-(N-morpholino)ethanesulfonic acid), 174t, 202–204 Mesh size, 535, 593, 646–647, 647t Mesitylene, 421p Mesityl oxide, 608i Metabisulfite, sodium, NR4 (9.10) Metabolism, 11, 556 Metal, in glass, 38p Metal dissolution, 651–652 Metal electrode, 301 Metal hydride battery, 295p Metal ion buffer, 316, 318 extraction, 504–505, 504d, 506b hydrolysis, 111, 111i indicator, 241–243, 241d, 242t, 243i natural water, 260 snow, 472p, 594m Metal-ligand equilibria, 238–241 Metaphosphoric acid, 652t Metasilicate, 21b Meter, 9t Methane: chemical ionization, 477 chromatography, 509 greenhouse gas, 426b isotopic composition, 482b protonated, 477i separation, 534 Methanesulfonate, hydration number, 140t Methanesulfonic acid hydration number, 140t Methanol: critical constants, 568t density, 17p diffusion coefficient, 513t eluent strength, 563t, 579i HPLC solvent, 576 oxidation, 138p pKa, 225p ultraviolet cutoff, 563t Methionine, 182t Method blank, 80 Method detection limit, 87 Method development: electrophoresis, 620 gas chromatography, 549–551 HPLC, 575–583 Method of continuous variation, 408–410 Method validation, 82 Methoxide, 106 Methyl acetamide hydration number, 140t Methylamine, 105, 140t, 229 Methylammonium chloride, 111 Methylammonium ion, 105 Methylarsonate, 94p Methyl borate, 653t, 654 N,NЈ-Methylenebisacrylamide, 441, 601i Methylene blue, 289t, 333t N-Methylformamide, 616 Methyl oleate, 520t Methyl orange, 215t 3-Methyl-2-pentanone, 496p 4-Methyl-2-pentanone, 483i Methyl red, 215t, 241d, 406i, 407 Methyl stearate, 520t Methyl t-butyl ether, 553p, 563t Methylthymol blue, 243i, 419p Methyl violet, 215t Metric ton, 11t Micellar electrokinetic chromatography, 83i, 615–618 Micelle, 422p, 423p, 504d, 598b, 615 Michelson, A., 443m Michelson-Morley experiment, 443m Micro, 10t Microarray, 397 Microbalance, quartz, NR1 (2.3) Microbe, 270 Microburet, 216b Microcantilever, 20 Micro cell, 384i Microdialysis, 556 Microelectrode, 369 Microequilibrium constant, 247p Microfluidic device, 621–622 Microliter pipet, 28i Micromechanical device, 20 Micropipet, 28–29 calibration, NR2 (2.18) Microporous particle, 559 Microreactor, 621 Microscale titration, 26 Microscopic description of chromatography, 522b Microscopy, electrochemical, 370 Microsphere, 439 Microwave: bomb, 125 digestion, 396, 651, 654 extraction, 656 oven, 31 radiation, 380i spectroscopy, 181i Migration, 361 Migration time, 610, 619 Mile, 11m, 18p Milk, 108i, 125t, 494b Milk of magnesia pH, 108i Milli, 10t Milliliter, 11t Millimeter Hg, 11t Mine, acid drainage, 96, 108i Mineral, 628 Minimum detectable concentration, 86 MINVERSE, 406 Mirror image spectra, 392i, 395i Miscibility, 502m Mitochondrion, 293p, 397 Mixed operations, uncertainty, 46 Mixing chamber, 539 Mixture, titration, 124, 131–132 I13 www.elsolucionario.org Mixture analysis, 402–406 mL (milliliter), 11t MMULT, 406 Mobile phase, 506 Mobility, 303, 487, 605–609 MOBS, 175t Modulation, 465 Mohr buret, 121 Mohr pipet, 27i Moisture removal, 31t mol, 9t, 12 Molality, 12 Molality–molarity conversion, 107t Molar absorptivity, 381 Molarity, 12, 32 Molarity–molality conversion, 107t Mole, 9t, 12, 16m Mole balance, 132 Molecular conductance, 273b Molecular exclusion chromatography, 507i, 508, 566i, 599–602 desalting, 600 gels, 600, 601i Kav, 600 molecular mass determination, 601 void volume, 600 Molecular imprinting, 441, 442i, 603b Molecular ion, 476, 477m, 478–483 Molecular light switch, 413 Molecularly imprinted polymer, 441, 442i Molecular mass, 12, 476b calibration standard, 602i determination, 601–602, 619 electrospray of proteins, 493–495 uncertainty, 49 Molecular orbital, 388 Molecular sieve, 534, 539i Molecular vibration, 389 Molecular wire, 273b Molybdenum, permanganate titration, 337t Monochromatic light, 381m, 382 Monochromator, 381 bandwidth, 431 dispersion, 430 emission, 394i excitation, 394i filter, 432–433 grating, 425i, 429–431 resolution, 430 slit, 425i Monoclonal antibody, 229, 602i, 603 Monodentate ligand, 229 Monohydrogen phosphate, 112 Monohydrogen phthalate, 185 Monolithic column, 562b, 588 Monoprotic system, 191 MOPS, 175t MOPSO, 175t, 308t Morphine, 197p, 586 4-(N-Morpholino)butanesulfonic acid, 175t 2-(N-Morpholino)ethanesulfonic acid, 174t, 202–204 3-(N-Morpholino)-2hydroxypropanesulfonic acid, 175t, 308t 3-(N-Morpholino)propanesulfonic acid, 175t Mortar, 2i, 650 Mother liquor, 30, 633m MTBE, 118p Mull, 384 Mullite mortar, 650 Multidentate ligand, 229 I14 Multielement detection, 463–464 Multiple flow paths, 520 Multiple regression with LINEST, 135 Multiplication: significant figures, 41 uncertainty, 45 Murexide, 242t, 243i Muscle, 180 Mussel, 470i Mylar beam splitter, 446 Myoglobin, 180i, 194b, 562i Myosin, 619i, 626p Myricetin, 580 Mysoline, 43b n (nano), 10t N (newton), 10t ␯ (frequency), 379 NADϩ, 441, 442 NADH, 289t, 321, 442 NADPϩ, 442 field effect transistor, 321 NADPH, 289t, 321 Nafion, 31t, 369, 374–375p, 482b Nano, 10t Nanometer, 380i Nanoparticle, 601 Naphtholphthalein, 215t 1-Naphthylammonium, 618i Naproxen, 658 Narcolepsy, 561i Naringenin, 580 Narrow-bore column, 550t National Fire Protection Association label, 21i, 22 National Institute of Standards and Technology, 43b pH reference buffers, 308t Natural gas, 544i Natural logarithm, 47 Natural water: acidity, 209b alkalinity, 209b ions, 596i metal ions, 260 Nebulization, 456, 457i Nebulizer, 488, 489i Negative pH, 214b Neocuproine, 387 Neon isotopes, 474m Nernst equation, 279 glass electrode, 307 ion-selective electrode, 312, 313, 315 Nerve cell, 228 Nessler’s reagent, 659t Neurotensin, 562i Neurotransmitter, 369, 604 Neutralization, 105 Neutral pH, 108 Neutral red, 215t Neutron mass, 479t Newton, 10, 10t Newton’s law, 18p Nickel vessel, 640 Nickel: crucible, 653t EDTA titration, 245 gravimetric analysis, 630t, 635 isotopes, 498p masking, 245 ore, 647 San Francisco Bay, 228 Nickel-63, 487 Nickel-metal hydride battery, 295p Nicolsky-Eisenman equation, NR7 (15.24) Nicotinamide adenine dinucleotides, 289t, 321, 441, 442 Nicotine, 206i, 208, 553p, 586p “Nines” (puritiy nomenclature), App K NIST traceable standard, App K Nitramine, 215t Nitrate: aquarium, 138p depolarizer, 355 dichromate titration, 339 field effect transistor, 321 gravimetric analysis, 630t lakes, 645i mass spectrometry, 554p ocean floor, 270 reduction, 336 Nitric acid: digestion, 651, 655 Ka, 159b oxidant, 328t role in gravimetric analysis, 634 strength, 108t, 214b Nitric oxide, 60, 250, 339b, 358b, 398p, 477, 554p Nitrides, 651 Nitrilotriacetic acid, 126m, 230i, 231i, 318, 593m Nitrite, 75p, 138p, 336, 343t, 401p, 452p, 554p, NR19 (28.25) p-Nitroaniline, 214b Nitrogen: air, 60 analysis, 638–640 atomic emission, 462, 464 bound, 339b chemiluminescence detector, 544, 549 detector, 544, 571t diffusion coefficient, 513t elemental analysis, 640 gas chromatography, 537–538 isotope abundance, 479t Kjeldahl analysis, 124–125, 654 liquid, 327 purification, NR10 (17.21) separation, 534 thermal conductivity, 542t Nitrogen dioxide, iodometric titration, 343t Nitrogen oxide, 336, 359b electrode, 316 Nitrogen-phosphorus detector, 543t, 544, 548i, 549 Nitrogen rule, 478 Nitromethane hydration number, 140t Nitron, 630t, 631t, 641p p-Nitrophenol, 215t 2-Nitrophenyl octyl ether, 315 1-Nitropropane, 537t 2-Nitropropane, 368i 1-Nitroso-2-naphthol, 630t, 631t Nitrous acid, permanganate titration, 337t Nitrous oxide (N2O), 60, 339b, 426b, 457t, 645i Noble gas, 19p Nobel Prize, 60, 228, 362i, 411m, 443m, 474m, 488m, 508m, 629, 629m, NR10 (18.1) Noise, 385, 448–449, 466i Nominal mass, 476b Nomograph, eluent strength, 579i Nonaqueous titration, 218, NR5 (11.19) Nonbonding electrons, 477i Nonbonding orbital, 388 Nonlinear calibration curve, 70i, 71b Nonlinear least-squares curve fitting, NR2 (4.6) Nonpolar, 228 Nonpolarizable electrode, 353 Nonsuppressed ion chromatography, 597 Nonwetting agent, 653 Norepinephrine, 572, 624p Normal alkane, 14 Normal distribution, 53m Normal error curve, 55 Normality, App E Normalization, 55 Normalized peak area, 607 Normal-phase chromatography, 563, 566i NORMDIST, 56 Nose, electronic, 360b Notebook, 22 NOx, 359b NTA (nitrolotriacetic acid), 126m, 230i, 231i, 318 N-terminal residue, 180 Nuclear energy, 415b Nucleation, 630 Nujol, 384 Null hypothesis, 59 Number, spaces in, 9m ⍀, 10t Oberlin College, 349m Occlusion, 633 Ocean, 12 CO2 sensor, 420p electricity generation, 270 pH, 96 Octadecyl bonded phase, 561, 579t Octadentate ligand, 229 Octanoic acid, 585 Octanol, 199m Octyl bonded phase, 561, 579t ODS (octadecylsilane), 561m Official Methods of Analysis, NR1 (0.6) Ohm (⍀), 10t, 273 Ohmic drop, 369 Ohmic potential, 352 Ohm’s law, 273 plot (electrophoresis), 610 Oil, 370 Oleum, 214b On-column injection, 540i, 541, 551 One-tail t-test, 64, 65m Open tubular column, 507, 510, 518m, 520, 529–534, 539i, 550 Open-circuit voltage, 350m Operator, Opium, 620 Opsin, 435b Optical fiber, 438 Optical isomer (see enantiomer) Optic nerve, 435b Optimization, 87, NR3 (5.8) Optode, 438–439 Optrode, 438 Orange peel, 545 Orbital, 388 Ordinate, 10 Ore, 647, 653 Organic carbon, 338b Organic material, dissolution, 654–655 Organic peroxide, dichromate titration, 339 Organic structures, 114 Organohalide determination, 139p Oscillating reaction, 302d Index Osmium tetroxide, 651 Osmolality blood test, 312t Outer cone, 457i Ovalbumin, 562i, 619i, 626p Overall formation constant, 104b, 239 Overloading (chromatography), 521, 570 Overpotential, 351, 351t, 354, 363 Ovotransferrin, 194b Oxalate: barium oxalate solubility, 260-262 homogeneous precipitant, 633t permanganate standardization, 337 precipitation titration, 134t transferrin binding, 138p Oxalic acid: acid dissociation, 112 buffer, 187–188 permanganate titration, 122, 337t principal species, 190 Oxaloacetate, 289t Oxidant, 271 Oxidation, 270, 271m catalyst, 638m catalytic, 338b, 339b number, App D organic material, 654–655 photochemical, 338b, 339b Oxidizing acid, 651 Oxidizing agent, 270, 652t Oxidizing strength, 279t Oxine, 346p, 504m, 631t Oxygen: blood test, 312t cell consumption, 416–417 COD, 376p cyclic voltammetry, 368i demand, 338b diffusion coefficient, 513t electrode, 358–359b elemental analysis, 640 formal potential, 289t indicator beads, 417i iodometric titration, 343t isotope abundance, 479t myoglobin binding, 180i optode, 438–439 overpotential, 351t oxidant, 328t polarographic waves, 364 pyrolysis analysis, 639 removal, 60, 364, 539i, NR10 (17.21) respiration, 379m sensor, 358–359b, 414i, 416–417 separation, 534 thermal conductivity, 542t zirconia O2 generator, NR9 (17.12) Ozone, 10, 10i, 328t, 339b, 343t, 400p, 426b Ozone hole, 10, 10i, 378, 379 p (pico), 10t P (peta), 10t Pa (pascal), 10t PAB ion exchanger, 591t Packed column, 507, 518m, 520, 534–535 Paired t-test, 62 Palladium, masking, 245 Palladium nitrate, 460 PAN, 440m Paper mill, 96 Parallax, 25 Parr oxidation, 654 Index Particle: growth (precipitate), 630–631 sampling, 646–650 size (in chromatography), 535, 557–558, 559t Partition chromatography, 507i, 508 Partition coefficient, 502, 510, 521 Partition ratio, 509m Parts per billion, 13 Parts per million, 13 Pascal, 10, 10t Passivation, App K Patent, 22m Pathlength, optical, 614i Patton & Reeder’s dye, 243i Pauling, L., 629m Peak: area measurement, 541–542 broadening (chromatography), 522b current, 367, 368i doubling (HPLC), 569 shape (electrophoresis), 612–613 Pee Dee belemnite, 482b Penetration depth, 440 Pentafluorobenzyl bromide, 554p Pentagonal bipyramidal coordination, 231i Pentane: eluent strength, 563t ultraviolet cutoff, 563t 2-Pentanone, 537t Pentobarbital, 477i Peptide bond, 180 Peptization, 634 Percent composition, 13 Percent transmittance, 381 Perchlorate, 87i, 316m, 630t Perchloric acid: density, 18p digestion, 652t, 655 hydrate, 106 oxidant, 328t precautions, 655 strength, 108t, 214b titrant in acetic acid, 218 use, NR19 (28.15) Perfluorokerosene, 481 Perflurotributylamine, 481 Performance test sample, 81 Perfusion blood test, 312t Periodate, 328t, 343t, 344p, 624p Permanent hardness, 245b Permanganate: dichromate titration, 339 iodometric titration, 343t oxalate titration, 122 oxidant, 328t, 336–337 spectrum, 419p titration, 332d Peroxide: catalytic decomposition, 396 dichromate titration, 339 flux, 653, 653t, 654 preoxidation, 335 Peroxyborate, 345p Peroxydisulfate, 328t, 335, 337t, 338b, 343t cleaning solution, 26, NR1 (2.13) Persian coin, 13, 14i Persistence of end point, 372 Persulfate (see peroxydisulfate) Pesticide, 321, 412, 533b, 546, 656, 658 Pestle, 2i, 650 Peta, 10t Pewter, 453 p Function, 127 pH, 108, 147 common substances, 108i critical care profile, 312t electrode (see glass electrode) fish survival, 108i fluorescent beads, 158 from cell voltage, 285–286 glass electrode, 306–311 intracellular, 158 iridium electrode, NR7 (15.14) measurement errors, 311 negative, 214b ocean, 96 pOH, 160 phosphorylation, 293p principal species, 190–191 scale, 108 standards, NR7 (15.16) uncertainty, 48 zero charge, 194–195, 197p Phagocytosis, 158 Phase boundary, 277 Phase diagram, 568b Phase transfer catalyst, 506b pH effects: affinity chromatography, 603 capillary electrophoresis, 607 EDTA complex formation, 234–235 enzyme reaction rate, 167i extractions, 503–504 formal potential, 289–291 molecular wire, 273b silica, 560, 561 Phenanthroline, 294p Phenobarbital, 43b, 627p Phenol, 111m, 142, 397 Phenolate, 111m, 142 Phenolphthalein, 213m, 215t, 383d Phenol red, 215t Phenosafranine, 333t Phenylalanine, 182t, 515i Phenyl bonded phase, 579t Phenylboronic acid, 441 Phenylhydrazine, 177p Phenylmethylpolysiloxane, 548 Phenyl stationary phase, 561 Phenytoin, 43b pH meter, 277d, 302d, 371d Beckman, 307m calibration, 308–309 history, NR7 (15.15) resistance, 284b terminals, 277m use, 308–309 US Standard connector, 277m pH of zero charge, 194–195, 197p Phosphate: buffer, 173, 576t gravimetric analysis, 630t permanganate titration, 337t precipitation titration, 134t protonated forms, 112 reference buffers, 308t Phosphide, 651 Phosphor, 391b Phosphorescence, 390–391 Phosphoric acid, 112, 174t, 175t, 652t Phosphorous acid, 341t Phosphorus: atomic emission, 462, 464 detector, 544, 548i flame photometric detector, 549 isotope abundance, 479t phosphomolybdate analysis, 643p Phosphorus pentoxide, 31t, 637 Phosphorylase, 619i, 626p Photoaction spectrum, 415b Photocell, 414b Photochemical oxidation, 339b Photoconductive detector, 437 Photodiode array, 434–436, 436t, 572, 572i Photoelectron spectroscopy, 477i Photoionization detector, 544, 549 Photomultiplier, 426, 433–434, 436t Photooxidation, 338–339b, 376p Photosynthesis, 415b Phototube, 433 Photovoltaic detector, 437 pH-sensitive field effect transistor, 321 pH-stat titration, 249p Phthalate, 185, 308t, 597 Phthalic acid, 185 Physical gel, 618 Phytoplankton, 500p Phytoremediation, 244m Pi bonding electrons, 477i Pickling, App K Pico, 10t Picolinic acid, 196p Picric acid, 418p Piezo alerting buzzer, 165d Piezoelectric crystal, 20, 460 Piezoelectric mixer, 621–622 Pigment separation, 506m Pinch clamp, 121 P ion exchanger, 591t Pi orbital, 388 PIPBS, 174t, 175t Piperazine, 162, 635 Piperazine-N,NЈ-bis(4-butanesulfonic acid), 174t Piperazine-N,NЈ-bis(2-ethanesulfonic acid), 174t, 175t Piperazine-N,NЈ-bis(3-propanesulfonic acid), 174t, 175t Piperidine, ionization energy, 477i PIPES, 174t, 175t Pipet, 27–29 bulb, 28 calibration, 33 tolerance, 27t, 29t uncertainty, 49–50 pi-pi interactions, 579t PIPPS, 174t, 175t Piranha solution, 651 Piston pump, HPLC, 570, 570i Pitzer equation, 144, NR4 (8.7) Pixel, 436 pK (pKa, pKb), 161 Gran plot, 212 principal species, 190–191 protein titration, 199 strong acids, 214b titration curve, 204i, 206i pKw, 161 0.1 M KCl, 265 Planck distribution, 427b Planck’s constant, 379 Plane angle, 9t Plane-polarized light, 379 Plankton, 500p Plant, 244m Plant pigment, 506m Plasma, 385, 453, 474 Plasma wave, 440 Plasmon, 440 Plaster, 245b Plasticizer, 304i Plate height, 514, 523b, 537i, 554p, 558i, 604, 609 Plate number, 558 Platform, L’vov, 458i I15 Platinum: diaphragm, 326i electrode, 299, 301, 302d, 354i, 574 masking, 245 potential range, 363m vessel, 651 PLOT, 529 Plutonium, 292p Pneumatically assisted electrospray, 488 Pneumatic nebulizer, 456 pn Junction, 319 pOH, 160 Poisson distribution, 423p, NR12 (19.23) Polar, 228 Polarity, 532t, 535i Polarizability, 592m Polarizable electrode, 353 Polarization, 413, 428 concentration, 352 Polarized light, 379 Polarogram, oscillation, 363m Polarographic wave, 363 Polarography, 362–364 apparatus, 363 ascorbic acid, 290i diffusion current, 364 dropping-mercury electrode, 362–363 half-wave potential, 290i, 363 oxygen waves, 364 polarographic wave, 363 residual current, 364 sampled current, 363 square wave, 364–366 stripping analysis, 366–367 wave shape, 364–366 Polar stratospheric clouds, 378, 379 Pollution, 244m Polonium-210, 477 Polyacrylamide, 441, 601i, 611m Polyalkylamine ion exchanger, 590t Polybasic species, 112 Polybutadiene, 519i Polychromatic light, 429m Polychromator, 435, 572i Polycyclic aromatic hydrocarbon, 397 Poly(diethylene glycol succinate), 520t Poly(dimethylsiloxane), 501 Polyethylene, 316, 384, 645, 651 Poly(ethylene glycol), 339b, 532t, 567 Polyimide, 529 Polymer: conductive, 360b molecularly imprinted, 441, 442i, 603b Polymerase chain reaction, 618, 621 Polypeptide, 180 Polypropylene flask, 27 Polyprotic acid, 112–114, 188–189 Polyprotic base, 112 Polyprotic fractional composition equations, 192m Polypyrrole, 360b Polysaccharide, 298i, 590, 591i Polysiloxanes, 532t Polystyrene, 447i, 559, 589, 589i, 590t, 601i, 602i Polytetrafluoroethylene, 644 Poly(vinyl chloride), 304i, 315 Ponceau, 418p Pooled standard deviation, 61 Population: inversion, 428 mean, 54 standard deviation, 54 I16 Porcelain, 650 Pore, size, 600 Porosity, 559i Porous carbon, 530i Porous graphitic carbon, 562 Porous-layer open tubular column, 529, 534 Port, injection, 539i Post-column derivatization, 572 Postprecipitation, 634 Potassium: blood test, 312t channel, 228 diffusion coefficient, 513t EDTA titration, 246p gravimetric analysis, 630t ion-selective electrode, 316m precipitation titration, 134t valinomycin complex, 304i Volhard titration, 134t Potassium bromate, 346p Potassium bromide: beam splitter, 446 infrared cutoff, 384m pellet, 384 Potassium chloride: density, 646 entropy of solution, 98 liquid junction, 303t salt bridge, 277 solubility, 102b Potassium cyanate, 633t Potassium dichromate: absorbance standard, 432t redox titrations, 339 spectrum, 383d Potassium dihydrogen citrate buffer, 308t Potassium hydrogen fluoride, 653 Potassium hydrogen iodate, 217t Potassium hydrogen phthalate, 185, 217t, 226, 308t Potassium hydrogen tartrate, 142, 308t Potassium hydroxide, 108t flux, 653, 653t solution preparation, 216 Potassium iodate, 340 Potassium iodide, 653 Potassium nitrate, 141, 646 Potassium permanganate, 332d, 336–337 Potassium peroxydisulfate, 338b Potassium pyrosulfate, flux, 653, 653t Potassium tetraphenylborate, 134t, 630t Potato chips, 662 Potential: cell membrane, 293p difference, 10t electric, 272 electrode conversion scale, 300 electrode range, 363m energy, 476b glass electrode, 307 half-cell, 280b, 282i ion-selective electrode, 305 ohmic, 352 standard, 277–279 zero charge, 365b Potential differences, 272, 274m Potentiometer, 275i, 277d, 302d Potentiometric titration: Gran plot, 334 precipitation, 131i, 301 redox, 332d Potentiometry, 299, 349 Potentiostat, 353 Potomac River, 96 Pound, 11m, 11t conversion to newton, 156p Pound per square inch, 11t Powder, grinding, 650 Power: calculator, 47m electric, 273 uncertainty, 47–48 units, 10t, 11t Power supply, 349i ppb, 13 ppm, 13 Practical-grade chemical, 123b Precambrian era, 628 Precipitant, 630 Precipitate composition, 634 electric charge, 133 Precipitation: crystal growth, 630–631 digestion, 633 electrolyte role, 632–633 filterability of product, 630 homogeneous, 631, 633t product composition, 634 separations, 101–102 titration, 127–134, 157p, 301 Precision, 39, 43, 54m, 81m atomic spectroscopy, 468t injection, 84 instrument, 84 interlaboratory, 84, 85b intermediate, 84 intra-assay, 84 Precolumn (guard column), 568 Preconcentration, 444m, 458, 492, 547, 594, 658–659 Precursor ion, 492 Prefix (multiplier), 10 Preheating region, 457i Premix burner, 456, 457i Preoxidation, 335 Preparation of sample, 547–549, 644–659 Preparative chromatography, 511, 569b Preparing solutions, 14–15 Prereduction, 336 Preservative, 335, 341 Pressure: critical, 568t equilibrium constant, 97 gas chromatography, 536 HPLC, 557–558, 559t, 576 programming, 536 units, 10, 10t, 11t Pressure broadening, 463 Primary amine, 111 Primary standard, 122, 123b, NR5 (11.17) acids and bases, 216, 217t buffer, 254 Primer, 618 Primidone, 43b Principal species, 190–191 Principle of Le Châtelier, 99–100 Prism, 429, 440 Procion Brilliant Blue M-R, 164b Product, 15m Product ion, 493 Proline, 182t Propagation of uncertainty, 44–50, App C addition and subtraction, 44–45, 49t calibration curve, 71 exponents, 49t logs, 49t mixed operations, 46 multiplication and division, 45, 49t standard addition, 90 x2, 48b Propane: hydration number, 140t thermal conductivity, 542t 2-Propanol: eluent strength, 563t ultraviolet cutoff, 563t 1-Propanol chromatography solvent, 568 Protein: aptamer assay, 413 arsenic sensor, charge ladder, 608, 626p colorimetric analysis, 69, 74p digestion, 167i food, 19p isoelectric focusing, 194b Kjeldahl analysis, 125 mass spectrometry, 493–495, 494b molecular mass, 619 sequence, 474 structure, 180 titration, 199 transferrin, 126, 385–387 Protein A, 602 Proteoglycan, 298i Protic solvent, 105, 107 Protocol, 82 Proton, 105 Protonated molecule, 477 Protonated methane, 477i Proton mass, 479t Pseudomonas bacteria, 138p psi (pounds per square inch), 11t Pt gauze electrode, 354i Pulsed electrochemical detector, 574 Pulse height, 364i Pump, 570, 570i Purge, septum, 539 Purge and trap, 548 Purified grade chemical, 123b Purity: “nines” nomenclature, App K precipitate, 633–634 reagent, 123b PVC, 339b Pyrene, 423p Pyrex, 26m, 33 Pyridine, 119p, 205, 537t Pyridinium, 119p, 251 Pyridoxal phosphate, 162 Pyridylazonaphtol, 243i 1-(2-Pyridylazo)-2-naphtol, 440m Pyridylazonapthol plus Cu-EDTA, 243i Pyrocatechol violet, 242t, 243i Pyroelectric effect, 437 Pyrogallol red, 243i Pyrolysis, 458, 639 Pyrolytic graphite, 458 Pyrophosphate, 635 Pyrophosphoric acid, 652t Pyrosulfate, flux, 653t Pyruvate, 289t QAE ion exchanger, 591t Q test, 65 Quadratic equation, 71b, 160m Quadrupole ion-trap mass spectrometer, 486 Quadrupole mass spectrometer, 484 Qualitative analysis, 5, 476 Quality assessment, 81b Quality assurance, 78–87 Quality control sample, 81 Quantitative analysis, Index www.elsolucionario.org Quantitative transfer, Quantum dot, 601–602 Quantum efficiency, 436 Quantum yield, 415 Quartz, 20 Quartz crystal microbalance, NR1 (2.3) Quartz-halogen lamp, 425 Quartz plate sieve, 619i Quaternary ammonium hydroxide, 108t Quaternary ammonium ion exchanger, 590t Quenching, 396, 414–416, 423p, 438 Quercitin, 580 Quinhydrone electrode, 296p Quinone, 296p rad (radian), 9t Radian, 9t Radiant flux, 10t Radiant power, 381m Radiationless transition, 390 Radiation treatment, 230 Radioactivity, 628, 629 Radioisotope, 230 Radio wave, 380i Radium, 629 Radium chloride, 629 Radius: hydrated, 140 hydrodynamic, 606 ionic, 140 Radon, 628 Rain, acid, 250, 260 Rainwater, 108i, 310b, 361, 385m Raman spectrum, 159b Ramp, voltage, 363 Random error, 43 Random heterogeneous material, 7b Random sample, 7b Random variable, 522b Random walk, 392 Range, 65, 84 dynamic, 71 linear, 71 Rare earth, 453 Raw data, 79 Rayleigh, Lord, 60 RDX, 487i Reactant, 15m Reaction quotient, 99, 279 Reagent blank, 80, 386 Reagent gas, 477, 487 Reagent-grade chemical, 123b Receptor, 602 transferrin, 291 Reciprocal centimeter, 379 Reconstructed total ion chromatogram, 491i, 492 Recycling, 21 HPLC solvent, 568m Red blood cell, 53 Redox indicator, 332–334, 333t Redox reaction, 270 balancing, App D Redox reagents, 328t Redox titrations, 327–343 calculating curve shape, 327–332, 332d cerium(IV), 337–339 dichromate, 339 end point, 331 Gran plot, 334 indicators, 332–334 iodine, 340–343 permanganate, 336–337 preoxidation, 335 Index prereduction, 336 procedures, NR8 (16.2) spreadsheet, 331m superconductor, 327, 342b, 346p, 347p Reducing agent, 271 Reducing strength, 279t Reductant, 271 Reduction, 271m Reduction catalyst, 638m Reduction potential: acid dissolution, 651 electron flow, 282i Latimer diagram, 282b relation to K, 284 standard, 277 tables, App H transferrin, 291 use of tables, 278–279 Reductor, 336 Referee, 480i Reference cell, 424 Reference cuvet, 384 Reference electrode, 299–301 calomel, 300, 329i conversion scale, 300 glass electrode, 131i, 301 silver-silver chloride, 300 symbol, 353i 3-electrode cell, 353 Reflection grating, 425i, 429 Reflectivity, 440i Reflectron, 485i, 486 Reflux cap, 654, 655i Refraction, 429, 437–438 Refractive index, 379, 437, 438m detector, 571t, 572–573 fused silica, 452p Refractory element, 457 Refractory material, 651 Regression (least squares), 65–69 Rejection of data, 65 Relative humidity, 37p Relative migration time, 619 Relative reference, 35 Relative retention, 509, 510 Relative standard deviation, 54 Relative uncertainty, 44 Releasing agent, 467 Remediation, 327m Renal function blood test, 312t Replicate measurement, 8, 649 Reporting limit, 87 Reporting results, Reprecipitation, 634 Representative sample, 7b, 644 Reproducibility, 84 Residence time, 457 Residual current, 354, 364 Residual sodium carbonate, 209b Resin, 508m, 589, 590m preconcentration, 658–659 Resistance, 273 electric, 10t, 273 glass electrode, 307 pH meter, 284b superconductor, 327 units, 10t Resistivity, NR8 (15.30) water, 594 Resolution: capillary electrophoresis, 604–605 chromatography, 511–512, 515–516, 579m, NR15 (23.8) electrophoresis, 610 FTIR, 445 gas chromatography, 530, 531, 538, 550m mass spectrometry, 478m monochromator, 467i spectroscopy, 430 Resolving power, 478 Respirator, 21 Response factor, 90, 542 Results, 79 conclusions, interpretation, reporting, Retardation, 445 Retention factor, 509m Retention gap, 538 Retention index, 535, 536m Retention time, 509 Retention volume, 511 Retina, 435b, 604 Retinal, 435b Retinol, 328t Reverse bias, 319 Reversed-phase chromatography, 563, 566i, 575–583 Reverse osmosis, 594 Reversible electrochemical reaction, 367 Rhodamine G, 392 Rhodopsin, 435b Riboflavin, 289t, 397 Ribonuclease, 199, 513t, 562i Ribonucleic acid (see RNA) Ribose, 614i Richards, T W., 628 Rich flame, 457, 467 Ring-down spectroscopy, 424 Rings and double bonds, 481 Ritalin, 561i, 587p River: bicarbonate content, 150b calcium content, 150b lead analysis, 78 sediment, 197p RMS noise, 448 RNA (ribonucleic acid), 199, 366t, 402, 413 Robustness, 87 Rock, 640 Rod cell, 435b Root (mathematics), 47 Root-mean-square (rms) noise, 448 Ross electrode, NR7 (15.22) Rotating disk electrode, 298, 361, 362i, 376p Rotational energy, 389 Rotational transition, 390 Rouleaux formation, 53i Round robin testing, 43m Rounding-off rules, 41 Ru(II): luminescence, 413, 416–417, 423p, 438 sensitizer, 414b Rubber, 316 glove, 21 policeman, 30 Rubidium, Rubidium hydroxide, 108t Rubidium sulfate, 544 Ruggedness, 84, 575 Rule of three, 577m, 587p Run buffer, 610 Ruthenium tetroxide, 651 Rutin, 580 s (second), 9t s (standard deviation), 54, 61, 68 ␴ (population standard deviation), 54 Σ (summation sign), 54 Safety, 20–22 Safety glasses, 21i Safranine T, 289t Salicylaldoxime, 631t Salicylate, 634 Salicylic acid, 162, 556, 586p Saliva pH, 108i Salt, 100m, 105 Salt bridge, 276, 277, 277d Salting out, 155p Sample: composite, 7b digestion, 651–655 injection (chromatography), 538–541, 551, 571, 571i loop, 571, 571i preconcentration, 658–659 preparation, 2, 3, 8, 547–549, 644–659 random, 7b selection, 7, 645 size for analysis, 648 storage, 645 Sampled current polarography, 363 Sample preparation, 492, 655–659 Sampling, 2, 7, 644, NR19 (28.16) constant, 648 direct solid, 459 statistics, 646–650 time, 363i variance, 646m Sandwich complex, 360m Sandwich injection, 538, 539i San Francisco Bay, 228 Sanger, F., 629m Sapphire, 384m, 570 Sarin, 548i Saturated calomel electrode, 300 Saturated solution, 100 Saturation fraction, 408 Scale, 245b Scale up: chromatography, 511, 557 gradient, 582b Scandinavia, 453 Scanning electrochemical microscopy, 370 Scanning tunneling microscope, 273b Scatchard plot, 407–408 S.C.E (saturated calomel electrode), 300 Schematic circuit diagram, 274i Schliera, 27 Scifinder, 2m SCOT, 529 Screen, 535 Seawater, 12, 108i, 420p, 459, 548i, 658, 662p Second, 9t Secondary amine, 111 Second derivative, 210–211 Second-order diffraction, 430 Sediment, 197p, 270, 459, 645i Segmented gradient, 565i, 580, 583 Segregated heterogeneous material, 7b SE ion exchanger, 591t Selected ion monitoring, 491–492, 491i, 545 Selected reaction monitoring, 491–493, 545 Selection of sample, 7, 645 Selectivity, 80 Selectivity coefficient: ion exchange, 591 ion-selective electrode, 312 Selenite, 396 Selenium: fluorescence assay, 396–397 isotopes, 470 I17 Self-absorption, 396, 468 Semiconductor, 318, 437 Semipermeable barrier, 277d Semipermeable membrane, 316, 556, 632d Semithymol blue, 419p Semi-xylenol orange, 137p Sensitivity, 80 balance, 22 gas chromatography, 543t HPLC detector, 571t Sensitizer, 414b Sensor: glucose, 357–361 heparin, 298, 315 oxygen, 358b Separation factor, 610 Separations, 501–523, 528–551, 556–583, 588–622, 655–659 adsorption chromatography, 508 affinity chromatography, 508, 602–603 capillary electrophoresis, 603–620 chromatography, 508 controlled-potential electrolysis, 353 enantiomers, 533b, 584p, 594, 603, 616i, NR16 (26.3) gas chromatography, 528–551 gel filtration, 508, 599–602 gel permeation, 508 high-performance liquid chromatography, 556–583 ion chromatography, 594–597 ion-exchange chromatography, 508, 589–594 isotopes, 615i molecular exclusion, 508, 599–602 molecularly imprinted polymer, 441, 442i, 603b partition chromatography, 508 precipitation, 101–102 preparative, 569b selecting HPLC separation mode, 566–567 solvent extraction, 502–506 Separator column, 594 Sephadex, 590, 591i, 600t Septum, 529, 539 purge, 539 Sequencing DNA, 618 Series expansion, 396 Serine, 182t, 344p Serum, 385, 658 Serum albumin, 513t, 609 Serum iron determination, 385–387 Servomotor, 22i Seven coordination, 234i Sewage, 96, 492–493 Shatterbox, 650, 651i S.H.E (standard hydrogen electrode), 278 Shell, 470i Shorthand (organic structures), 114 Shower, 22 Siemens, 273b Sieve, 647t molecular, 534 Sieving, 618, 619i Sigma bonding electrons, 477i Sigma orbital, 388 Signal averaging, 448 Signal detection limit, 86 Signal-to-noise ratio, 448, 466i monochromator, 431 Significant figure: addition and subtraction, 40–41 graphs, 42 least-square parameters, 68 I18 logarithms and antilogarithms, 41–42 mean and standard deviation, 55 multiplication and division, 41 real rule, 46 zeros, 40 Silanization, 521, 561m Silanol, 531, 560, 606 Silica: acidity, 194–195 chromatography, 4, 559i, 560i, 600 fluorescent beads, 416 fused, 384, 529 gel, 31t grating protective layer, 429 hydrolysis, 519i, 561 monolithic column, 562b stationary phase, 579t Silica capillary preparation, 610 Silica gel, 392 Silicate, 307i, 640, 653 Silicon: charge coupled device, 436–437 isotope abundance, 479t photodiode array, 434–436 photoresponse, 433i semiconductor, 318 Silicon cantilever, 20 Silicon carbide, 427, 459, 640 Silicon dioxide, 320 Silicone breast implant, 501 Silicon nitride, 320i, 640 Silicon tetrafluoride, 640 Siloxane, 501, 532t, 560i Silurian era, 628 Silver: adsorption on Teflon, 645 bromide, 314t coins, 13, 14i cyanide equilibria, 266p, 268p EDTA titration, 244 electrode, 131i, 301–302 field effect transistor, 320–321 iodide, 314t iodide equilibria, 119p ion-selective electrode, 314, 316m masking, 245 permanganate titration, 337t reducing agent, 336 stripping analysis, 366t sulfide, 314, 314t thiocyanate, 314t vessel, 651 Silver(II), 335, 357 Silver chloride: colloidal particle, 632i electric charge, 133 equilibria, 116p infrared window, 384m ion-selective electrode, 314t light sensitivity, 134 solubility in KCl, 311 Silver-silver chloride electrode, 300 combination electrode, 306 Simplex optimization, 87, NR3 (5.8) Simultaneous equations, 405–406 Single-beam spectrophotometer, 381i, 384, 424 Single-column ion chromatography, 597 Single-molecule spectroscopy, 392 Singlet state, 388, 416 Sintering, 414b SI units, 9–11 Size, particle, 535 Size distribution, nebulizer, 457i Skimmer cone, 489i Skin cancer, 10 Skin disease, Slit, monochromator, 425i Slope, App B least-squares calculation, 66–67 titration curve, 129, 210 SLOPE (Excel), 67 Slurry, 3, 30 Smallest titration, 216b Smith, John, 39 Smoke, 323p, 659 Snell’s law, 438 Snow, 472p, 594m Soap, 245b Sodium: channel, 228 critical care profile, 312t diffusion coefficient, 513t dispersion, 139p D line, 437 error, 311 ion-selective electrode, 316m mobility in glass, 307 vision, 435b Sodium aluminosilicate, 534i Sodium azide, 564i Sodium bicarbonate, 124 Sodium bismuthate, 335 Sodium bisulfite, NR4 (9.10) Sodium borate, flux, 653, 653t Sodium carbonate: flux, 653, 653t primary standard, 217t, 227 residual, 209b titration, 124, 225p Sodium chloride: infrared cutoff, 384m ion pair, 143b liquid junction, 303t matrix, 459 ocean, 12 Sodium D line, 437 Sodium dodecyl sulfate, 422p, 615m Sodium dodecyl sulfate-gel electrophoresis, 619i Sodium hydrogen carbonate, 124 Sodium hydrogen sulfite, 21b Sodium hydroxide: equilibrium, 119p flux, 653, 653t preparation, 216 reaction with glass, 216 standardization, 226–227 strong electrolyte, 108t Sodium hypochlorite, 19p, 169 Sodium metabisulfite, NR4 (9.10) Sodium metasilicate, 21b Sodium nitrate in HPLC, 576 Sodium octyl sulfate, 624p Sodium oxalate, 337 Sodium peroxide, flux, 653, 653t, 654 Sodium peroxyborate, 345p Sodium sulfate ion pair, 143b Sodium tetraphenylborate, 631t, 642p Sodium thiosulfate, 340–341, NR9 (16.22) Soft drink, 6t Soil, 244m, 412, 656 Solar energy, 414–415b, 426b Solid, standard state, 97 Solid angle, 9t Solid-phase extraction, 492, 644, 658 Solid-phase microextraction, 547–548 Solid-state chemical sensor, 318–321 Solid-state ion-selective electrode, 316m Solomon, S., 379 Solubility: calcium sulfate, 151–153 common ion effect, 101 Eº, 285 ionic-strength effect, 141–142 ligand-concentration effect, 103i lithium fluoride, 156p magnesium hydroxide, 153–154 metal complexes, 504–505 minerals, 260 separations, 101–102 solubility product, 100, 285, App F Solute, 12 polarity, 532t standard state, 97 Solution preparation, 14–15 Solvent, 12 additive (HPLC), 568 chromatography, 563, 564m, 568 front, 574, 575 sample, 569 standard state, 97 triangle, 577i, 578i water content, 568 Solvent extraction, 502–506 crown ether, 506b distribution coefficient, 503, 505 dithizone, 504d, 505i efficiency, 502–503 metal chelator, 504–505, 504d, 506b pH effect, 503–504 partition coefficient, 502 strategies, 505 Solvent trapping, 540 SOLVER, 253, 265, 404, 421p Soman, 548i Sonication, 366 Sørenson, S P L., 168m Source: field effect transistor, 320 spectrophotometer, 426–428 South Pole, 10i Soybean trypsin inhibitor, 194b Space focus plane, 485i, 486 Space shuttle, 293p Sparkman, O D., 478m Species, 8m Specific adsorption, 365b Specification, 79 Specific gravity, 13m Specificity, 80, 82 Spectral interference, 467 Spectral width, FTIR, 446 Spectrometer, ion mobility, 487–488 Spectronic 20 spectrophotometer, 40 Spectrophotometer, 424–437 atomic absorption, 455i atomic spectroscopy, 462–466 cuvet, 384 detector, 433–437 dispersive, 435 double-beam, 384, 425 emission, 394i filter, 432–433 Fourier transform (FTIR), 442–448 light sources, 426–428 monochromator, 429–433 photodiode, 435 single-beam, 381i, 384, 424 Spectronic 20, 40 stray light, 432 Varian Cary 3E, 425i Spectrophotometric titration, 126, 410i Spectrophotometry, 379 absorption of light, 380–383, 383d accuracy, 384–385 Index analysis of mixture, 402–406 Beer’s law, 381, 382b, 402 detectors, 433–437 dispersion, 430 double-beam, 425i emission, 380i, 383d, 390–391, 392–397 equilibrium constant measurement, 407–408 errors, 385 flow injection analysis, 410–411 fluorescence, 383d, 390–391, 392–397 Fourier transform, 442–448 grating, 429–431 isosbestic point, 406, 419p Job’s method, 408 luminescence, 392–397 method of continuous variation, 408–410 phosphorescence, 390–391 properties of light, 379–380 resolution, 430 Scatchard plot, 407–408 serum iron determination, 385–387 signal averaging, 448 time-resolved fluorescence, 412 titration, 410i Spectroscopy, single-molecule, 392 Spectrum, 380, 380i, 383d blackbody, 426b, 427b Speed of light, 9m, 379, 443m Sphalerite, 249p Spherogel, 601i Spike, 80, 492 Spike recovery, 80 Spills, 22 SP ion exchanger, 591t Spleen, 603 Split injection, 539, 540i, 551 Splitless injection, 539–541, 551 Split point, 539i Split ratio, 539 Split vent, 540i Spreadsheet: absolute reference, 35 acid-base titration, 218–221, 221t ADD-INS (Excel), 64 ANALYSIS TOOL PACK, 64 arithmetic operations, 34 auxiliary complexing agent, 248p AVERAGE, 55 BINOMDIST, 555p binomial distribution, 555p cell, 33 CHART, 35–36, 51p, 72 circular reference, 156p, 269p complex formation, 247p DATA ANALYSIS, 64 documentation, 35 EDTA titration, 237–238 formula, 34 function, 34 GOAL SEEK, 115, 154, 176 graphing, 35–36, 51p intercept, 68–69 INTERCEPT (Excel), 67 introduction, 33–36 iteration, 156p label, 34 least squares, 71–72 LINEST, 68–69, 83, 135 matrix, 68–69 matrix functions, 405–406 MINVERSE, 406 MMULT, 406 naming cells, 176 NORMDIST, 56 Index number, 34 order of operations, 35 parentheses, 35 pooled variance, 64 precipitation titrations, 132, 139p redox titrations, 331m relative reference, 35 SLOPE, 67, 68–69 SOLVER, 253, 265, 404, 421p solving equations, 115 solving linear equations, 405–406 standard deviation, 55 STDEV, 55 TOOLS, 64 TRENDLINE, 72 t test, 64–65 trial-and-error solution, 115 variance, 64–65 Square, uncertainty, 48b Square wave polarography, 364–366 Squaric acid, 110b sr (steradian), 9t Stability constant, App I cell voltage, 287–288 EDTA complexes, 234t Stacking, 612–613, 616 Stadium analogy for luminescence, 392 Staircase: voltage ramp, 363 wave, 364i Stallion, 184 Standard: acids and bases, 226–227 analytical, App K elemental assay, App K matrix matched, 470 matrix matching, App K NIST traceable, App K pH, 308t solution, 5, 69, 122, 466 state, 97, 98f stoichiometry, App K test sieve, 647t ultraviolet absorbance, 432t ultraviolet/visible wavelength, NR12 (20.9) Standard addition, 87–90, 317, 467 Standard curve, Standard deviation, additivity, 517m chromatography, 522b diffusive broadening, 514 F test, 63–64 Least-squares parameters, 68–69 measure of experimental error, 44 pooled, 61 sampling, 646–650 Standard enthalpy change, 98 Standard HCl, 217t, 225p, 227 Standard hydrogen electrode, 278 Standardization, 122, 226–227 Standard operating procedure, 81, 82 Standard reduction potential, 277, 280b equilibrium constant, 284 Latimer diagram, 282b measurement, 295p relation to equilibrium constant, 284 tables, App H use of tables, 278–279 Standard Reference Material, 43b, 80, 84, 122, NR2 (3.1) Stannic chloride, 651 Stannous chloride, 336, 456b Stannous ion, 328t Starch, 334–335, 340 Stationary phase, 506 bonded, 531 chiral, 584p gas chromatography, 531, 532t HPLC, 579t ion exchange, 589–591 liquid chromatography, 559–562 molecular exclusion, 600, 601i Statistics, 53–72 1-tailed test, 64, 65m, NR2 (4.5) 2-tailed test, 64, 65m, NR2 (4.5) comparison of means, 59–62 confidence interval, 57–59 detection limit, 84–87 F test, 63–64 Gaussian distribution, 53–57 least-squares, 65–69 linear regression, 65–69 Q test, 65 rejection of data, 65 sampling, 646–650 standard deviation, 62, 67–69 Student’s t, 57–62, 64–65 STDEV (Excel), 55 Steel mortar, 650 Stefan-Boltzmann constant, 426b Step height, 363i Steps in chemical analysis, 7–8 Stepwise formation constants, 104b, 239m, App I Steradian, 9t Stern layer, 365b Stern-Volmer equation, 416i Steroid, 658 Stimulated emission, 428 Stirring bar, 122i Stirring motor, 122i Stochastic theory, 522b Stoichiometry, 16–17, 16m, 408–410 standards, App K Stokes equation, 605 Stopcock, 121 Storage: chemicals, 22 dilute solutions, 318m sample, 645 St Paul’s Cathedral, 250 Straight line graph, 65–69, App B Strata, 628 Stratosphere, 378 Stray light, 432 Streamlined calculation, titration, 128 Streptomyces pilosus, 232b Stretching, molecular, 389i Stripping analysis, 366–367 Strong acid, 109 pH calculation, 159–161 reaction with weak base, 170b titration of strong base, 200–201 titration of weak base, 205–206 Strong base, 109 pH calculation, 159–161 reaction with weak acid, 170b titration of strong acid, 200–201 titration of weak acid, 202–204 Strong electrolyte, 12 Strongly acidic ion exchanger, 589, 590t Strongly basic ion exchanger, 589, 590t Strontium, 337t, 467–468 Strontium hydroxide, 109t Strutt, J W., 60 Student (W S Gosset), 57m Student’s t: comparison of means, 59–62, 64–65 confidence interval, 57–59 table, 58t Styrene, 589i Sublimation, 568b Substituent, 180, 181 Subtraction: significant figures, 40–41 uncertainty, 44–45 Successive approximations, 152m, 186b Succinate, 144, 289t Succinic acid, 117p Sucrose: chromatography, 506m diffusion coefficient, 513t electrophoresis, 614i Sugar, 18p, 257, 341t, 348, 533b, 599i, 614i Sulfamic acid, 137p, 217t, 633t Sulfanilic acid, 401p, 420p Sulfate: acid mine drainage, 108i copper equilibria, 269p EDTA titration, 245 formal potential, 289t gravimetric analysis, 630t homogeneous precipitant, 633t ocean floor, 270 precipitation titration, 134t Sulfide: EDTA titration, 245, 249p gas trapping, 659t homogeneous precipitant, 633t ion-selective electrode, 314, 314t ocean floor, 270 precipitation titration, 134t volatility, 651 Sulfite, 346p, 375p analysis, 659t buffer demonstration, 171d clock reaction, 171d formal potential, 289t reductant, 328t Sulfonic acid, ion exchange, 590t Sulfosalcylic acid, 217t Sulfur: analysis, 638–640, 643p atomic emission, 462, 464 detector, 543t, 544, 544i flame photometric detector, 549 isotope abundance, 479t Sulfur chemiluminescence detector, 543t, 544, 549 Sulfur dioxide: acid rain, 260, 310b blood test, 312t electrode, 316 emissions, 250 food preservative, 375p gas trapping, 659t iodimetric titration, 341t Karl Fischer titration, 370 prereduction, 336 reductant, 328t trapping gas, 659t Sulfur hexafluoride, 479 Sulfuric acid: digestion, 125, 652t drying agent, 31 strength, 108t, 214b Sulfurous acid, 310b Sulfur oxides, 638 Summation sign, 54 Sunset yellow, 418p “Super acid,” 214b Superconductor, 327, 342b, 346p, 347p, 642p Supercritical fluid, 568b chromatography, 568b extraction, 656, 657i Superficially porous particle, 562 I19 www.elsolucionario.org Supernatant liquid, Supernate, 386m Supersaturation, 630 Support-coated open tubular column, 529, 529i Suppressed-ion chromatography, 594–597 Suppressor column, 594–595, 597 Surface acidity, 194–195 Surface area, silica, 559i Surface plasmon resonance, 440–442 Surface tension, 598b Surfactant, 504d, 598, 598b, 611, 616 Suspension, 630 Sweeping, 616–618 Sweep rate, cyclic voltammetry, 368 Symbol: approximately, 16m approximately equal to, 11m electrodes, 353i implies that, 15m Symmetric bend, 389i Symmetric stretch, 389i Synapse, 435b Synge, R L M., 508m Syringe, 29, 539, 571m, 644 “sandwich” injection, 538, 539i Systematic error, 42–43, 310b Karl Fischer titration, 371 propagation of uncertainty, 49–50 Systematic treatment of equilibrium, 147–154, 250–262 precipitation titration, 132 strong acids and bases, 160–161 weak acids, 163 Système International d’Unités, T (tera), 10t Tabun, 548i Tailing, 521, 531, 560i, 565, 569 Tanaka, K., 488m Tare, 22 Target value, 81b Tartaric acid, 238i, 251 Tartrate, 142, 594m Tartrazine, 418p, 632d Taylor cone, 489i TC (to contain), 26 TD (to deliver), 26 Tea, 6t TEAE ion exchanger, 591t Technical-grade chemical, 123b TEEN, 174t, 175t Teeth, 453, 456b Teflon, 118p, 122i, 316, 358b, 534, 644, 645, 651 Teflon bomb, 651, 654 Television, toxic waste, NR1 (2.4) TEMN, 175t Temperature: atomic spectroscopy, 461–462 buffer, 173, 174f, 308t chromatography, 519, 536, 579 climatic changes, 395b critical, 568t Earth, 426b, 427b equilibrium constant, 99–100 flame, 457t gravimetric analysis, 631 molarity of solution, 12, 32 ocean, 500p pH measurement, 311 plasma, 460i programming, 536 thermal conductivity detector, 542 units, 9t, 11t volume of glassware, 31–33 volume of water, 32t, 33 I20 Template, 603b Temporary hardness, 245b Tenax, 548m Tera, 10t Terbium, fluorescence, 572 Terrestrial diet, 528 Terror, 121 Tertiary amine, 111 TES (N-tris(hydroxymethyl) methyl-2-aminoethanesulfonic acid), 175t Tesla coil, 460 Test strip, Testosterone, 366t Tetraalkylamonium salt, ion pair, 165f Tetraborate, 653 Tetrabromofluorescein, 134 Tetrabutylammonium hydroxide, 108t, 218 Tetrabutylammonium ion, 599i Tetrabutylammonium salt, ion pair, 165f Tetracyanonickelate, 138p, 244 Tetradentate ligand, 229 Tetraethylammonium salt, ion pair, 165f N, N,N,NЈ-Tetraethylenediamine dihydrochloride, 174t N,N,NЈ,NЈ–Tetraethylethylmethylenediamine dihydrochloride, 175t Tetrafluoroethylene, 118p Tetrahydrofuran: eluent strength, 563t, 579i HPLC solvent, 576 storage, NR16 (25.24) ultraviolet cutoff, 563t Tetrakis [3,5-bis(trifluoromethyl) phenyl] borate, 315 Tetramethylammonium hydroxide, 119p Tetramethylammonium salt, ion pair, 165f Tetramethylrhodamine, 158 Tetraphenylarsonium chloride, 631t Tetraphenylborate, 134t, 246p, 304, 630t, 631t Tetrapropylamonium salt, ion pair, 165f Tetrathionate, 293p, 340 Thalassemia, 232b Theobromine, 2, 6t Theophylline, 603b Theoretical performance of column, 554p Theoretical plate, 514, 523b, 558, 559t, 604, 609 Thermal cell, 384i Thermal conductivity, 542 detector, 542, 543t, 549, 638 Thermal desorption, 548–549 Thermal expansion, 12, 31–33 Thermistor, 318i Thermocouple, 437 Thermodynamic data, NR3 (6.5) Thermodynamic prediction, 100 Thermodynamics, 98–99 Thermogravimetric analysis, 634, 642p Thick-film column, 550t Thin-film column, 550t Thioacetamide, 633t Thiocyanate: Fe(III) complex, 141, 421p gravimetric analysis, 630t ion-selective electrode, 314t iron complexes, 267p precipitation titration, 134t Volhard titration, 133 Thioglycolic acid, 341t, 386 Thiol, 273b Thiopental, 627p Thiosulfate, 293p, 328t, 340–341 anhydrous standard, NR9 (16.22) Thiourea, 245, 387 Thorium, permanganate titration, 337t Threonine, 182t, 344p Thrombosis, 298 Thymol, 335 Thymol blue, 213, 215t, 419p Thymolphthalein, 215t Thymolphthalein complexone, 243i Thyroxine, 397 Time, 9t Time-of-flight mass spectrometer, 481, 485–486, 494b Time-resolved fluorescence immunoassay, 412 Tin: capsule for elemental analysis, 639 flame photometric detector, 549 food content, 473p gravimetric analysis, 630t iodometric titration, 341t reductant, 328t Tin can, 473p Tin chloride, 336 Tin(II) chloride, 456b Tin(IV) chloride, 651 Titanium: gravimetric analysis, 630t masking, 245 permanganate titration, 337t Titanium dioxide, 338b, 339b, 376p, 414b Titanium(III), 357 Titanium(IV) spectrum, 403i Titrant, 121 Titration, 121 acid-base, 124, 199–221, 306m acid-base spreadsheet, 218–221, 221t argentometric, 133 autotitrator, 209 auxiliary complexing agent, 238–241 back, 244 blank, 122 blurred end point, 208 calculation for redox titration, 327–332, 332d cerium(IV), 337–339 complexometric, 129m, 230, NR6 (12.19) derivatives, 210–211 dichromate, 339 diprotic system, 206–208 direct, 122, 244 displacement, 244 EDTA, 229–245, 410i EDTA end point, 241–243 effect of concentration, 205i end point, 122, 129, 133–134, 208, 241d, 410i error, 122 Fajans, 133–134, 134t glass electrode, 306m Gran plot, 334 indirect, 244, 339 iodine, 340, 341t, 343t Karl Fischer, 370–372 mass, 26, NR1 (2.14) microscale, 26 mixture, 124, 131–132 nonaqueous, 218, NR5 (11.19) permanganate, 336–337 pH-stat, 249p pK effect, 205i, 206i potentiometric, 131i, 327–332, 332d precipitation, 127–134 primary-standard acids and bases, 216, 217t principles, 122 protein, 199 record small, 216b redox, 327–343, NR8 (16.2) redox indicators, 332–334 spectrophotometric, 126, 410i stoichiometry calculations, 123–124 techniques with EDTA, 244–245 Volhard, 133, 134t weak acid–strong base, 202–204 weak acid–weak base, 218–219 weak base–strong acid, 205–206 Titrator, 25i, 26, 209 Titrimetric analysis, history, NR18 (27.1) tm (chromatography), 575 TNT, 402, 422p, 487i ␣-Tocopherol, 328t Tolerance, 24, 31 buret, 25t micropipet, 29t pipet, 27t volumetric flask, 27t weights, 24t Toluene: eluent strength, 563t ultraviolet cutoff, 563t use, 502f Tomato juice pH, 108i Ton, 11t Tooth: atomic analysis, 453 decay, 257 enamel, 94p Torch, plasma, 460 Torr, 11t Total carbon, 338b Total organic halide (TOX), 373p Total oxygen demand, 338b TOX, 373p Toxin, 412 Trace, Trace analysis, 123b, 645 Trace metal grade chemical, 123b Trace metal grade HNO3, 470 Transfer pipet, 27–28 Transferrin, 126, 138p, 247p, 291, 385–386, 417p Transformer oil, 370 Transfusion, 232b Transistor, 318i, 320–321 Transition, 388 rotational, 390 vibrational, 390 Transition range: acid-base indicator, 213, 215, 215t redox indicator, 332, 333t Transmission quadrupole mass spectrometer, 484 Transmittance, 381, 382b, 424 Spectronic 20 scale, 40i Transversely heated furnace, 458 Trap, mercury, 456b Treated data, 79 Tree ring, 427b TRENDLINE (Excel), 72 Triangle, solvent, 577i, 578i Trichloroacetic acid, 386 Trichlorotrifluoroethane, 563t TRICINE, 174t, 175t Tridodecylmethylammonium chloride, 315 Triethanolamine, 238i, 245 Triethylamine, 560i, 569 Triethylammonium acetate, 569 Trifluoroacetic acid, 110b, 214b, 560i Index Triiodide, 340 Trimethylammonium chloride, 165 Trimethylphosphate, 633t Trimethylsilyl derivative, 528i Trinitrotoluene, 422p Trioctylphosphine, 602i Triple point, 9t, 568b Triplet state, 388, 416 Triprotic acid, 114, 188–189, 191i, 221t TRIS, 169, 174t, 175t, 217t Tris (2-aminoethyl) amine, 268p Tris(2,2Ј-bipyridine)iron, 333t Tris(2,2Ј-bipyridine)ruthenium(II), 333t, 423p Tris(hydroxymethyl aminomethane), 169, 174t, 175t, 217t N-Tris(hydroxymethyl)methyl-2aminoethanesulfonic acid, 175t N-Tris(hydroxymethyl)methylglycine, 174t, 175t Tris(5-nitro-1,10-phenanthroline)iron, 333t Tris(1,10-phenanthroline)iron, 333t Trititrotoluene, 402 Tritium, 307 Triton X-100, 504d Tropaeolin O, 215t Tryptophan, 182t TSK silica, 600t Tswett, M S., 506m t Test, 59–62, 64–65, NR2 (4.5) Tumor, 74p, 229–230 Tungsten, 337t, 459 Tungsten carbide, 650, 651 Tungsten lamp, 426, 426i, 571 Tungsten trioxide, 467, 638 Turbidity, 131m Two-tail t-test, 64, 65m Tylenol, 360 Type A silica, 560 Type B silica, 560 Type C silica, 560 Tyrosine, 182t, 199 Ulcer, 424 Ultrapure acid, 123b Ultrasonic mixing, 622 Ultrasonic nebulizer, 460 Ultrasonic vibration, 366 Ultraviolet: absorbance standard, 432t cutoff, 563t detector, 571, 571t, 613 radiation, 10, 338b, 378, 380i Uncertainty, 44–50, 58, App C calibration curve, 71 confidence interval, 58 exponents, 47–48 least-squares parameters, 68–69 logarithms, 47–48 molecular mass, 49 pipet, 49–50 principle, 462 propagation, 49t sampling, 646–650 standard addition, 90 x-intercept, 90 Uncle Wilbur, 400p Unified atomic mass unit, 476b Unit matrix, 406 Units, 11 Units of measurement, 9–11 Unmentionables, 391b Uracil, 576 Uranium, 337t, 628 Urea, 120p, 218, 424, 631, 633t Uric acid, 360 Index Urine, 108i, 123, 553p, 655, 658 Use objective, 79 Volumetric analysis, 121 Volumetric flask, 14, 14i, 26–27 V (volt), 10t Vacancy, 313i Vacuum desiccator, 31i Vacuum pump, 537 Vacuum tube, 307m Vacuum ultraviolet, 462 Valine, 182t Valinomycin, 304 Vanadium(V) oxide, 651 Vanadium(V) spectrum, 403i Vanadate, 630t Vanadyl sulfate, 623p van Deemter equation, 517, 538 electrophoresis, 604–605 experimental graph, 518i, 537i, 558i, 627p micellar electrokinetic chromatography, 627p Variable voltage source, 349i Variamine blue B base, 243i Varian Cary E3 spectrophotometer, 425i Variance, 54 additivity, 517, 646 F test, 63–64 Vascular disease, Vasodilator, Vector, 406 Velocity, electroosmotic, 607m, 609 Ventilation blood test, 312t Vernier scale, 51p Vesicle, 18p, 604 Vessel: digestion, 651, 655 extraction, 657i Vibration, molecular, 389 Vibrational frequency, 20 Vibrational relaxation, 390 Vibrational states, 390–391 Vibrational structure, 393 Vibrational transition, 390 Vicinal silanol groups, 560i Vinegar pH, 108i Virginia Polytechnic Institute, 277d Viscosity, 558, 605, 607 Visible light, 380i Vision, 435b Vitamin A, 328t, 435b Vitamin C, 232b, 289t, 290i, 343, 360 formal potential, 289–291 Vitamin E, 328t Void volume, 600 Vol%, 13 Volatile buffers, 574 Volatile electrolyte, 634 Volhard titration, 133, 134t Volt, 10t, 272 Voltage, 272 breakdown, 319m capillary electrophoresis, 609, 610 open circuit, 350m ramp, 363 scale, 300 source, 349i unit, 10t Voltaic cell, 274 Voltammetry, 362–370 Voltammogram, 362 Voltmeter, 277 Volume: column, 600 flow rate, 508 gravimetric analysis, 631 units, 11t Volume percent, 13 W (watt), 10t Waage, P., 97m Walden reductor, 336 Wall-coated open tubular column, 529 Warning line, 81b Waste: disposal, 21b, 576m, NR1 (2.5) reduction in HPLC, 568m remediation, 327m Wastewater, 228r, 338b Watchglass, 31i Water: acid-base effect on dissociation, 161 analysis, 1, 596i arsenic removal, 634m carbon dioxide content, 108 coordination, 140 critical constants, 568t density, 32t, 33 diffusion coefficient, 513t distillation, 645t electrolysis, 350d expansion, 31–33 hardness, 209b, 245b, 594m infrared absorption, 394 ion chromatography, 596i ionization, 150–151, 161 irrigation, 209b, 245b isotopic molecules, 394 Karl Fischer titration, 370–372 lead, 466i metal content impurities, 504d pH, 108 “polishing,” 594 potential range, 563t purity, 564m refractive index, 438m resistivity, 594 softener, 594m solvation of ions, 140 temperature dependence of Kw, 107t thermal expansion, 31–33 triple point, 9t water of hydration, 140 Watt, 10t, 273 Waveform, 367i Waveguide, 439–440 Wavelength, 379 color, 380i selection for analysis, 384 Wavenumber, 379 WCOT, 529 Weak acid, 110–114 conjugate, 167 diprotic, 181–188 fraction of dissociation, 164, 191–192 intermediate form, 184 pH calculation, 162–166 polyprotic, 188–189 reaction with strong base, 170b titration with strong base, 202–204 titration with weak base, 218–219 Weak base, 110–114 pH calculation, 166–167 reaction with strong acid, 170b titration with weak acid, 218–219 Weak electrolyte, 12, 164, 165d Weakly acidic ion exchanger, 589, 590t Weakly basic ion exchanger, 589, 590t Weighing bottle, 23, 31i Weighing errors, 23–24 Weighing procedure, 22–24 Weight: effect of altitude, 37p tolerance of lab standards, 24t Weight percent, 13 Wenzel, T., Weston cell, 374p Wet ashing, 650, 654 Wetterhahn, K., 21m Whistle noise, 449 White blood cell, 158 White chocolate, 6t White light, 435 Whitener, 391b White noise, 448 Wide-bore column, 550t Wig-L-Bug, 650, 651i Wind power, 415b Wine, 346p, 375p Work, 10t, 272–273 Working electrode, 349, 353 potential range, 363m rotating disk, 361, 362i Wright, W.H., 307m Wt%, 13 x (mean value), 54 Xanthine, 289t Xenon lamp, 571 X-Gal, x-intercept, 90 X-ray, 380i p-Xylene in iodine titrations, 340m Xylenol orange, 210i, 242t, 243i, 419p y (yocto), 10t Y (yotta), 10t Yalow, R., 411m Yeast, 194b, 439 YO, 467i Yocto, 10t Yoctomole, Yotta, 10t Yttrium-90, 230 Yttrium aluminum garnet, 431i Yttrium barium copper oxide, 327, 342b, 467i, 642p Yttrium hydroxychloride, 642p Yttrium oxide, 642p z (multiple of standard deviation), 55 z (zepto), 10t Z (Zetta), 10t Zarontin, 43b Zeeman effect, 466 Zeolite, 534i Zepto, 10t Zeptomole, Zeros, 40 Zetta, 10t Zinc: ammonia complexes, 239 EDTA titrations, 244 electrode, 302 gravimetric analysis, 630t hydroxide complexes, 119p impurity in tungsten, 459 iodimetric titration, 341t Jones reductor, 336 masking, 245 permanganate titration, 337t precipitation titration, 134t spectrophotometric analysis, 504d Zinc sulfate reagent, 123b Zirconia, 519i, 650 Zirconia oxygen sensor, 359b Zone broadening, electrophoresis, 609 Zorbax silica, 560i Zwitterion, 181 Zwitterionic bonded phase, 567i I21 www.elsolucionario.org Physical Constants Term Symbol Value Faraday constant (ϭ Ne) Boltzmann’s constant (ϭ R/N) F k 1.987 207 (4) 9.648 533 83 (83) 1.380 650 (24) Electron rest mass me 9.109 382 (16) Proton rest mass mp 1.672 621 71 (29) Dielectric constant (permittivity) of free space Gravitational constant ␧0 8.854 187 817 ϫ 10Ϫ19 C ϫ 10Ϫ10 esu ϫ 108 m/s ϫ 1010 cm/s ϫ 10Ϫ34 J и s ϫ 10Ϫ27 erg и s ϫ 10Ϫ34 J и s ϫ 10Ϫ27 erg и s ϫ 1023 molϪ1 J/(mol и K) V и C/(mol и K) ϫ 10Ϫ2 L и bar/(mol и K) ϫ 107 erg/(mol и K) ϫ 10Ϫ5 m3 и atm/(mol и K) ϫ 10Ϫ2 L и atm/(mol и K) cal/(mol и K) ϫ 104 C/mol ϫ 10Ϫ23 J/K ϫ 10Ϫ16 erg/K ϫ 10Ϫ31 kg ϫ 10Ϫ28 g ϫ 10Ϫ27 kg ϫ 10Ϫ24 g ϫ 10Ϫ12 C2/(N и m2) G 6.674 (10) ϫ 10Ϫ11 m3/(s2 и kg) (14)† Elementary charge e Speed of light in vacuum c 1.602 176 53 4.803 204 40 (42) 2.997 924 58 Planck’s constant h 6.626 069 (11) h/2␲ ប 1.054 571 68 (18) Avogadro’s number Gas constant N R 6.022 141 (10) 8.314 472 (15) 8.205 746 (15) †Numbers in parentheses are the one-standard-deviation uncertainties in the last digits SOURCE: P J Mohr and B N Taylor, 2002 CODATA values, from http://physics.nist.gov/constants (June 2004) Concentrated Acids and Bases Name Approximate weight percent Molecular mass Approximate molarity Approximate density (g/mL) mL of reagent needed to prepare L of ϳ1.0 M solution Acid Acetic Hydrochloric Hydrofluoric Nitric Perchloric Phosphoric Sulfuric 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 Base Ammonia† Sodium hydroxide Potassium hydroxide 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− HA + OH− → A− + H2O 12 Equivalence point A− + H2O HA + OH− F' − x 10 x x x2 = Kb F' − x Excess OH− Kw pH = − log [OH−] pH Buffer region [A−] pH = pK a + log [HA] Initial point HA H+ + A− F−x x x x2 = Ka F−x 10 20 30 Volume of base added (Vb ) 40 50 60 Titration of weak base B with strong acid H+ 11 B + H+ → BH+ Initial point B + H2O BH+ + OH− F−x x x pH x2 = Kb F−x Excess H+ Buffer region [B] pH = pK a + log [BH+] pH = − log [H+] Equivalence point B + H+ BH+ F' − x x x x2 = Ka F' − x 10 20 30 Volume of acid added (Va ) 40 50 60 ... Quantity of electricity, electric charge Electric potential, potential difference, electromotive force Electric resistance Electric capacitance hertz newton pascal joule watt coulomb volt ohm... Quantitative Chemical Analysis [“The Experiment” by Sempe © C Charillon, Paris.] www.elsolucionario.org Quantitative Chemical Analysis SEVENTH EDITION Daniel C Harris Michelson Laboratory China... in a chemical reaction It is derived from the Greek stoicheion (simplest component) and metiri (to measure) ϪO C H C C CO2Ϫ H Let’s apply concepts from preceding sections to a chemical analysis