Christian7e ffirs.tex V1 - 08/16/2013 2:53 P.M Page i Christian7e ffirs.tex V1 - 08/16/2013 2:53 P.M Page i ANALYTICAL CHEMISTRY SEVENTH EDITION Gary D Christian University of Washington Purnendu K (Sandy) Dasgupta University of Texas at Arlington Kevin A Schug University of Texas at Arlington Christian7e ffirs.tex V1 - 08/16/2013 2:53 P.M Page ii To Nikola from Gary—for your interests in science You have a bright future,wherever your interests and talents take you Philip W West from Sandy—wherever you are Phil, sipping your martini with ppm vermouth, you know how it was: For he said, I will give you, A shelter from the storm Dad from Kevin—well its not hardcore P Chem., but it is still quite useful Thanks for your love, support, and guidance through the years VP & Publisher: Editorial Assistant: Senior Marketing Manager: Designer: Associate Production Manager: Petra Recter Ashley Gayle/Katherine Bull Kristine Ruff Kenji Ngieng Joyce Poh This book was set in 10.5 Times Roman by Laserwords Private Limited and printed and bound by Courier Kendallville The cover was printed by Courier Kendallville This book is printed on acid free paper Founded in 1807, John Wiley & Sons, Inc has been a valued source of knowledge and understanding for more than 200 years, helping people around the world meet their needs and fulfill their aspirations Our company is built on a foundation of principles that include responsibility to the communities we serve and where we live and work In 2008, we launched a Corporate Citizenship Initiative, a global effort to address the environmental, social, economic, and ethical challenges we face in our business Among the issues we are addressing are carbon impact, paper specifications and procurement, ethical conduct within our business and among our vendors, and community and charitable support For more information, please visit our website: www.wiley.com/go/citizenship Copyright © 2014, 2004 John Wiley & Sons, Inc All rights reserved No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc 222 Rosewood Drive, Danvers, MA 01923, website www.copyright.com Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030-5774, (201)748-6011, fax (201)748-6008, website http://www.wiley.com/go/permissions Evaluation copies are provided to qualified academics and professionals for review purposes only, for use in their courses during the next academic year These copies are licensed and may not be sold or transferred to a third party Upon completion of the review period, please return the evaluation copy to Wiley Return instructions and a free of charge return mailing label are available at www.wiley.com/go/returnlabel If you have chosen to adopt this textbook for use in your course, please accept this book as your complimentary desk copy Outside of the United States, please contact your local sales representative Library of Congress Cataloging-in-Publication Data Christian, Gary D., author Analytical chemistry Seventh edition / Gary D Christian, University of Washington, Purnendu K (Sandy) Dasgupta, University of Texas at Arlington, Kevin A Schug, University of Texas at Arlington pages cm Includes index ISBN 978-0-470-88757-8 (hardback : alk paper) Chemistry, Analytic Quantitative Textbooks I Dasgupta, Purnendu, author II Schug, Kevin, author III Title QD101.2.C57 2014 543 dc23 2013019926 Printed in the United States of America 10 Christian7e ftoc.tex V1 - 08/20/2013 8:30 A.M Page iii Contents Chapter Analytical Objectives, or: What Analytical Chemists Do 1.1 What Is Analytical Science?, 1.2 Qualitative and Quantitative Analysis: What Does Each Tell Us?, 1.3 Getting Started: The Analytical Process, 1.4 Validation of a Method—You Have to Prove It Works!, 15 1.5 Analyze Versus Determine—They Are Different, 16 1.6 Some Useful Websites, 16 Chapter Basic Tools and Operations of Analytical Chemistry 20 2.1 The Laboratory Notebook—Your Critical Record, 20 2.2 Laboratory Materials and Reagents, 23 2.3 The Analytical Balance—The Indispensible Tool, 23 2.4 Volumetric Glassware—Also Indispensible, 30 2.5 Preparation of Standard Base Solutions, 42 2.6 Preparation of Standard Acid Solutions, 42 2.7 Other Apparatus—Handling and Treating Samples, 43 2.8 Igniting Precipitates—Gravimetric Analysis, 48 2.9 Obtaining the Sample—Is It Solid, Liquid, or Gas?, 49 2.10 Operations of Drying and Preparing a Solution of the Analyte, 51 2.11 Laboratory Safety, 57 Chapter Statistics and Data Handling in Analytical Chemistry 62 3.1 Accuracy and Precision: There Is a Difference, 62 3.2 Determinate Errors—They Are Systematic, 63 3.3 Indeterminate Errors—They Are Random, 64 3.4 Significant Figures: How Many Numbers Do You Need?, 65 3.5 Rounding Off, 71 3.6 Ways of Expressing Accuracy, 71 3.7 Standard Deviation—The Most Important Statistic, 72 3.8 Propagation of Errors—Not Just Additive, 75 3.9 Significant Figures and Propagation of Error, 81 3.10 Control Charts, 83 3.11 The Confidence Limit—How Sure Are You?, 84 3.12 Tests of Significance—Is There a Difference?, 86 3.13 Rejection of a Result: The Q Test, 95 3.14 Statistics for Small Data Sets, 98 3.15 Linear Least Squares—How to Plot the Right Straight Line, 99 3.16 Correlation Coefficient and Coefficient of Determination, 104 3.17 Detection Limits—There Is No Such Thing as Zero, 105 3.18 Statistics of Sampling—How Many Samples, How Large?, 107 3.19 Powering a Study: Power Analysis, 110 3.20 Use of Spreadsheets in Analytical Chemistry, 112 3.21 Using Spreadsheets for Plotting Calibration Curves, 117 iii Christian7e ftoc.tex V1 - 08/20/2013 8:30 A.M CONTENTS iv 3.22 Slope, Intercept, and Coefficient of Determination, 118 3.23 LINEST for Additional Statistics, 119 3.24 Statistics Software Packages, 120 Chapter Good Laboratory Practice: Quality Assurance and Method Validation 132 4.1 What Is Good Laboratory Practice?, 133 4.2 Validation of Analytical Methods, 134 4.3 Quality Assurance—Does the Method Still Work?, 143 4.4 Laboratory Accreditation, 144 4.5 Electronic Records and Electronic Signatures: 21 CFR, Part 11, 145 4.6 Some Official Organizations, 146 Chapter Stoichiometric Calculations: The Workhorse of the Analyst 149 5.1 Review of the Fundamentals, 149 5.2 How Do We Express Concentrations of Solutions?, 152 5.3 Expressions of Analytical Results—So Many Ways, 159 5.4 Volumetric Analysis: How Do We Make Stoichiometric Calculations?, 166 5.5 Volumetric Calculations—Let’s Use Molarity, 169 5.6 Titer—How to Make Rapid Routine Calculations, 179 5.7 Weight Relationships—You Need These for Gravimetric Calculations, 180 Chapter General Concepts of Chemical Equilibrium 6.1 Chemical Reactions: The Rate Concept, 188 6.2 Types of Equilibria, 190 6.3 Gibbs Free Energy and the Equilibrium Constant, 191 6.4 Le Chˆatelier’s Principle, 192 6.5 Temperature Effects on Equilibrium Constants, 192 6.6 Pressure Effects on Equilibria, 192 6.7 Concentration Effects on Equilibria, 193 6.8 Catalysts, 193 6.9 Completeness of Reactions, 193 6.10 Equilibrium Constants for Dissociating or Combining Species—Weak Electrolytes and Precipitates, 194 6.11 Calculations Using Equilibrium Constants—Composition at Equilibrium?, 195 6.12 The Common Ion Effect—Shifting the Equilibrium, 203 6.13 Systematic Approach to Equilibrium Calculations—How to Solve Any Equilibrium Problem, 204 6.14 Some Hints for Applying the Systematic Approach for Equilibrium Calculations, 208 6.15 Heterogeneous Equilibria—Solids Don’t Count, 211 6.16 Activity and Activity Coefficients— Concentration Is Not the Whole Story, 211 6.17 The Diverse Ion Effect: The Thermodynamic Equilibrium Constant and Activity Coefficients, 217 Chapter Acid–Base Equilibria 188 222 7.1 The Early History of Acid—Base Concepts, 222 7.2 Acid–Base Theories—Not All Are Created Equal, 223 7.3 Acid–Base Equilibria in Water, 225 7.4 The pH Scale, 227 7.5 pH at Elevated Temperatures: Blood pH, 231 7.6 Weak Acids and Bases—What Is the pH?, 232 7.7 Salts of Weak Acids and Bases—They Aren’t Neutral, 234 7.8 Buffers—Keeping the pH Constant (or Nearly So), 238 7.9 Polyprotic Acids and Their Salts, 245 7.10 Ladder Diagrams, 247 7.11 Fractions of Dissociating Species at a Given pH: α Values—How Much of Each Species?, 248 7.12 Salts of Polyprotic Acids—Acid, Base, or Both?, 255 Page iv Christian7e ftoc.tex V1 - 08/20/2013 8:30 A.M CONTENTS v 7.13 Physiological Buffers—They Keep You Alive, 261 7.14 Buffers for Biological and Clinical Measurements, 263 7.15 Diverse Ion Effect on Acids and Bases: c Ka and c Kb —Salts Change the pH, 266 7.16 log C—pH Diagrams, 266 7.17 Exact pH Calculators, 269 Chapter Acid–Base Titrations 9.5 Other Uses of Complexes, 336 9.6 Cumulative Formation Constants β and Concentrations of Specific Species in Stepwise Formed Complexes, 336 Chapter 10 Gravimetric Analysis and Precipitation Equilibria 281 8.1 Strong Acid versus Strong Base—The Easy Titrations, 282 8.2 The Charge Balance Method—An Excel Exercise for the Titration of a Strong Acid and a Strong Base, 285 8.3 Detection of the End Point: Indicators, 288 8.4 Standard Acid and Base Solutions, 290 8.5 Weak Acid versus Strong Base—A Bit Less Straightforward, 290 8.6 Weak Base versus Strong Acid, 295 8.7 Titration of Sodium Carbonate—A Diprotic Base, 296 8.8 Using a Spreadsheet to Perform the Sodium Carbonate—HCl Titration, 298 8.9 Titration of Polyprotic Acids, 300 8.10 Mixtures of Acids or Bases, 302 8.11 Equivalence Points from Derivatives of a Titration Curve, 304 8.12 Titration of Amino Acids—They Are Acids and Bases, 309 8.13 Kjeldahl Analysis: Protein Determination, 310 8.14 Titrations Without Measuring Volumes, 312 Chapter Complexometric Reactions and Titrations 322 9.1 Complexes and Formation Constants—How Stable Are Complexes?, 322 9.2 Chelates: EDTA—The Ultimate Titrating Agent for Metals, 325 9.3 Metal–EDTA Titration Curves, 331 9.4 Detection of the End Point: Indicators—They Are Also Chelating Agents, 334 342 10.1 How to Perform a Successful Gravimetric Analysis, 343 10.2 Gravimetric Calculations—How Much Analyte Is There?, 349 10.3 Examples of Gravimetric Analysis, 353 10.4 Organic Precipitates, 353 10.5 Precipitation Equilibria: The Solubility Product, 355 10.6 Diverse Ion Effect on Solubility: Ksp and Activity Coefficients, 361 Chapter 11 Precipitation Reactions and Titrations 366 11.1 Effect of Acidity on Solubility of Precipitates: Conditional Solubility Product, 366 11.2 Mass Balance Approach for Multiple Equilibria, 368 11.3 Effect of Complexation on Solubility: Conditional Solubility Product, 372 11.4 Precipitation Titrations, 374 Chapter 12 Electrochemical Cells and Electrode Potentials 12.1 What Are Redox Reactions?, 384 12.2 Electrochemical Cells—What Electroanalytical Chemists Use, 384 12.3 Nernst Equation—Effects of Concentrations on Potentials, 390 12.4 Formal Potential—Use It for Defined Nonstandard Solution Conditions, 394 12.5 Limitations of Electrode Potentials, 395 383 Page v Christian7e ftoc.tex V1 - 08/28/2013 2:26 P.M Page vi CONTENTS vi Chapter 13 Potentiometric Electrodes and Potentiometry 399 13.1 Metal Electrodes for Measuring the Metal Cation, 400 13.2 Metal–Metal Salt Electrodes for Measuring the Salt Anion, 401 13.3 Redox Electrodes—Inert Metals, 402 13.4 Voltaic Cells without Liquid Junction—For Maximum Accuracy, 404 13.5 Voltaic Cells with Liquid Junction—The Practical Kind, 405 13.6 Reference Electrodes: The Saturated Calomel Electrode, 407 13.7 Measurement of Potential, 409 13.8 Determination of Concentrations from Potential Measurements, 411 13.9 Residual Liquid-Junction Potential—It Should Be Minimized, 411 13.10 Accuracy of Direct Potentiometric Measurements—Voltage Error versus Activity Error, 412 13.11 Glass pH Electrode—Workhorse of Chemists, 413 13.12 Standard Buffers—Reference for pH Measurements, 418 13.13 Accuracy of pH Measurements, 420 13.14 Using the pH Meter—How Does It Work?, 421 13.15 pH Measurement of Blood—Temperature Is Important, 422 13.16 pH Measurements in Nonaqueous Solvents, 423 13.17 Ion-Selective Electrodes, 424 13.18 Chemical Analysis on Mars using Ion-Selective Electrodes, 432 Chapter 14 Redox and Potentiometric Titrations 14.1 First: Balance the Reduction–Oxidation Reaction, 437 14.2 Calculation of the Equilibrium Constant of a Reaction—Needed to Calculate Equivalence Point Potentials, 438 14.3 Calculating Redox Titration Curves, 441 14.4 Visual Detection of the End Point, 445 14.5 Titrations Involving Iodine: Iodimetry and Iodometry, 447 437 14.6 Titrations with Other Oxidizing Agents, 452 14.7 Titrations with Other Reducing Agents, 454 14.8 Preparing the Solution—Getting the Analyte in the Right Oxidation State before Titration, 454 14.9 Potentiometric Titrations (Indirect Potentiometry), 456 Chapter 15 Voltammetry and Electrochemical Sensors 466 15.1 Voltammetry, 467 15.2 Amperometric Electrodes—Measurement of Oxygen, 472 15.3 Electrochemical Sensors: Chemically Modified Electrodes, 472 15.4 Ultramicroelectrodes, 474 15.5 Microfabricated Electrochemical Sensors, 474 15.6 Micro and Ultramicroelectrode Arrays, 475 Chapter 16 Spectrochemical Methods 477 16.1 Interaction of Electromagnetic Radiation with Matter, 478 16.2 Electronic Spectra and Molecular Structure, 484 16.3 Infrared Absorption and Molecular Structure, 489 16.4 Near-Infrared Spectrometry for Nondestructive Testing, 491 16.5 Spectral Databases—Identifying Unknowns, 493 16.6 Solvents for Spectrometry, 493 16.7 Quantitative Calculations, 494 16.8 Spectrometric Instrumentation, 504 16.9 Types of Instruments, 519 16.10 Array Spectrometers—Getting the Entire Spectrum at Once, 522 16.11 Fourier Transform Infrared Spectrometers, 523 16.12 Near-IR Instruments, 525 16.13 Spectrometric Error in Measurements, 526 16.14 Deviation from Beer’s Law, 527 16.15 Fluorometry, 530 16.16 Chemiluminescence, 538 16.17 Fiber-Optic Sensors, 540 Christian7e ftoc.tex V1 - 08/20/2013 8:30 A.M CONTENTS Chapter 17 Atomic Spectrometric Methods vii 548 17.1 Principles: Distribution between Ground and Excited States—Most Atoms Are in the Ground State, 550 17.2 Flame Emission Spectrometry, 553 17.3 Atomic Absorption Spectrometry, 556 17.4 Sample Preparation—Sometimes Minimal, 567 17.5 Internal Standard and Standard Addition Calibration, 567 17.6 Atomic Emission Spectrometry: The Induction Coupled Plasma (ICP), 569 17.7 Atomic Fluorescence Spectrometry, 574 Chapter 18 Sample Preparation: Solvent and Solid-Phase Extraction 20.1 20.2 20.3 20.4 20.5 20.6 20.7 20.8 20.9 20.10 20.11 579 Distribution Coefficient, 579 Distribution Ratio, 580 Percent Extracted, 581 Solvent Extraction of Metals, 583 Accelerated and Microwave-Assisted Extraction, 585 18.6 Solid-Phase Extraction, 586 18.7 Microextraction, 590 18.8 Solid-Phase Nanoextraction (SPNE), 593 19.1 Countercurrent Extraction: The Predecessor to Modern Liquid Chromatography, 598 19.2 Principles of Chromatographic Separations, 603 19.3 Classification of Chromatographic Techniques, 604 19.4 Theory of Column Efficiency in Chromatography, 607 19.5 Chromatography Simulation Software, 616 21.1 21.2 21.3 21.4 21.5 21.6 21.7 21.8 21.9 21.10 21.11 596 649 High-Performance Liquid Chromatography, 651 Stationary Phases in HPLC, 654 Equipment for HPLC, 665 Ion Chromatography, 692 HPLC Method Development, 700 UHPLC and Fast LC, 701 Open Tubular Liquid Chromatography (OTLC), 702 Thin-Layer Chromatography, 702 Electrophoresis, 708 Capillary Electrophoresis, 711 Electrophoresis Related Techniques, 724 Chapter 22 Mass Spectrometry 22.1 22.2 22.3 22.4 619 Performing GC Separations, 620 Gas Chromatography Columns, 623 Gas Chromatography Detectors, 630 Temperature Selection, 638 Quantitative Measurements, 639 Headspace Analysis, 641 Thermal Desorption, 641 Purging and Trapping, 642 Small and Fast, 643 Separation of Chiral Compounds, 644 Two-Dimensional GC, 645 Chapter 21 Liquid Chromatography and Electrophoresis 18.1 18.2 18.3 18.4 18.5 Chapter 19 Chromatography: Principles and Theory Chapter 20 Gas Chromatography 735 Principles of Mass Spectrometry, 735 Inlets and Ionization Sources, 740 Gas Chromatography–Mass Spectrometry, 741 Liquid Chromatography–Mass Spectrometry, 746 22.5 Laser Desorption/Ionization, 750 22.6 Secondary Ion Mass Spectrometry, 752 22.7 Inductively Coupled Plasma–Mass Spectrometry, 753 Page vii Christian7e ftoc.tex CONTENTS viii 22.8 Mass Analyzers and Detectors, 753 22.9 Hybrid Instruments and Tandem Mass Spectrometry, 764 Chapter 23 Kinetic Methods of Analysis Available on textbook website: www.wiley.com/college/christian Chapter G Century of the Gene—Genomics and Proteomics: DNA Sequencing and Protein Profiling G1 769 23.1 Kinetics—The Basics, 769 23.2 Catalysis, 771 23.3 Enzyme Catalysis, 772 Chapter 24 Automation in Measurements 24.1 24.2 24.3 24.4 24.5 24.6 784 Principles of Automation, 784 Automated Instruments: Process Control, 785 Automatic Instruments, 787 Flow Injection Analysis, 789 Sequential Injection Analysis, 791 Laboratory Information Management Systems, 792 G.7 G.8 G.9 G.10 G.11 G.12 Of What Are We Made?, G1 What Is DNA?, G3 Human Genome Project, G3 How Are Genes Sequenced?, G5 Replicating DNA: The Polymerase Chain Reaction, G6 Plasmids and Bacterial Artificial Chromosomes (BACs), G7 DNA Sequencing, G8 Whole Genome Shotgun Sequencing, G11 Single-Nucleotide Polymorphisms, G11 DNA Chips, G12 Draft Genome, G13 Genomes and Proteomics: The Rest of the Story, G13 APPENDIX A LITERATURE OF ANALYTICAL CHEMISTRY Chapter 25 Clinical Chemistry C1 25.1 Composition of Blood, C1 25.2 Collection and Preservation of Samples, C3 25.3 Clinical Analysis—Common Determinations, C4 25.4 Immunoassay, C6 EN1 Getting a Meaningful Sample, EN1 Air Sample Collection and Analysis, EN2 Water Sample Collection and Analysis, EN9 Soil and Sediment Sampling, EN11 Sample Preparation for Trace Organics, EN12 Contaminated Land Sites—What Needs to Be Analyzed?, EN12 26.7 EPA Methods and Performance-Based Analyses, EN13 794 APPENDIX B REVIEW OF MATHEMATICAL OPERATIONS: EXPONENTS, LOGARITHMS, AND THE QUADRATIC FORMULA 797 APPENDIX C TABLES OF CONSTANTS Available on textbook website: www.wiley.com/college/christian Chapter 26 Environmental Sampling and Analysis G.1 G.2 G.3 G.4 G.5 G.6 Available on textbook website: www.wiley.com/college/christian 26.1 26.2 26.3 26.4 26.5 26.6 V1 - 08/20/2013 8:30 A.M 801 Table C.1 Dissociation Constants for Acids, 801 Table C.2a Dissociation Constants for Basic Species, 802 Table C.2b Acid Dissociation Constants for Basic Species, 803 Table C.3 Solubility Product Constants, 803 Table C.4 Formation Constants for Some EDTA Metal Chelates, 805 Table C.5 Some Standard and Formal Reduction Electrode Potentials, 806 Available on textbook website: www.wiley.com/college/christian APPENDIX D SAFETY IN THE LABORATORY S1 Page viii Christian7e a06.tex V2 - 08/13/2013 8:54 A.M Page 812 ANSWERS TO PROBLEMS 812 15 10.01 mg CaCO3 /mL EDTA CHAPTER 11 16 10.01 (mg CaCO3 /L · H2 O)/mL EDTA s = 2.1 × 10−4 M; [IO3 − ] = 1.5 × 10−4 M; [HIO3 ] = 6.9 × 10−5 M 17 2.89 × 10 ppm s = 6.1 × 10−3 M; [HF] = 1.20 × 10−2 M; [F− ] = 8.01 × 10−5 M 18 9.93 mg/dL; 4.95 meq/L 19 98.79% s = 2.7 × 10−15 M; [H2 S] = 2.7 × 10−5 M; [HS− ] = 2.7 × 10−10 M; [S2− ] = 2.9 × 10−18 M 20 3.04 ppm 21 119 mg/L s = 8.4 × 10−3 M; [Ag(en)+ ] = 5.96 × 10−5 M; [Ag(en)2 + ] = 8.4 × 10−3 M 22 20.4 % [Ag+ ] = 1.8 × 10−4 M (2.1 × 10−4 M if include HIO3 formation) CHAPTER 10 [Pb2+ ] = 2.7 × 10−5 M 10 16.2 g 8.4 × 10−3 M = s (7.0 × 10−3 M if correct for en consumed by reiteration) 11 82.2 g 12 0.2138, 1.902, 0.1314, 0.6474 10 5.434 g/L 13 0.586 g 11 0.029 mL excess titrant 14 98.68% 12 Yes 15 0.6888 g 16 1.071% 17 636 mg CHAPTER 12 18 26 mL O3 , HClO, Hg2+ , H2 SeO3 , H3 AsO4 , Cu2+ , Co2+ , Zn2+ , K+ 19 1.75% 10 Ni, H2 S, Sn2+ , V3+ , I− , Ag, Cl− , Co2+ , HF 20 24.74 g 11 (a) Fe2+ − MnO4 − (b) Fe2+ − Ce4+ (HClO4 ) (c) H3 AsO3 − MnO4 − (d) Fe3+ − Ti2+ 21 2.571 g 22 42.5% Ba, 37.5% Ca 12 (a) VO2+ /Sn2+ (b) Fe(CN)6 3− /Fe2+ (d) I2 /I2 (e) H2 O2 /Fe2+ 23 79.98% 24 0.846 g AgCl, 1.154 g AgBr 25 (a) Ksp = [Ag+ ][SCN− ] (b) Ksp = [La3+ ][IO3 − ]3 (c) Ksp = [[Hg2 2+ ][Br− ]2 (d) Ksp = [Ag+ ][[Ag(CN)2 − ] (e) Ksp = [Zn2+ ]2 [Fe(CN)6 4− ] (f) Ksp = [Bi3+ ]2 [S2− ]3 26 8.20 × 10−19 −4 M Ag , 6.5 × 10 −8 M 27 1.3 × 10 28 1.9 × 10 + −5 M CrO4 2− 29 1.3 × 10−17 M 30 5.1 × 10−7 M, 1.0 × 10−9 M 31 3.8 34 AB : s = × 10−9 M, AC2 : s = × 10−6 M 35 Bi2 S3 is × 107 times more soluble than HgS! 36 0.33 M excess F− needed Is feasible 39 4.1 × 10−4 g 14 (a) Pt/Fe2+ , Fe3+ //Cr2 O7 2− , Cr3+ , H+ /Pt (b) Pt/I− , I2 //IO3 − , I2 , H+ /Pt (c) Zn/Zn2+ //Cu2+ /Cu (d) Pt/H2 SeO3 , SeO4 2− , H+ //Cl2 , Cl− /Pt 15 (a) 2V2+ + PtCl6 2− = 2V3+ + PtCl4 2− + 2Cl− (b) Ag + Fe3+ + Cl− = AgCl + Fe2+ (c) 3Cd + ClO3 − + 6H+ = 3Cd2+ + Cl− + 3H2 O (d) 2I− + H2 O2 + 2H+ = I2 + H2 O 16 1.24V 17 0.419 V 19 0.216 V 33 1.7 × 10−6 M 38 2.0 × 10−5 M 13 15.62% 18 0.65 V 32 1.4 × 10−6 M 37 (a) Ksp fBa2+ fSO4 2− (c) Ag+ /Cu (b) Ksp fAg+ fCrO4 2− 20 PtCl6 2− + 2V2+ = PtCl4 2− + 2V3+ + 2Cl− , 0.94 V 21 (a) 0.57 V (b) 0.071 V (c) 0.09 V 22 2VO2 + + U4+ = 2VO2+ + UO2 2+ , 0.67 V 23 0.592 V 24 (1) Cu: 0.286 V; Ag: 0.740 V; cathode (3) 0.277 V; anode (2) 0.706 V; cathode Christian7e a06.tex V2 - 08/13/2013 8:54 A.M Page 813 CHAPTER 17 813 16 4.96 meq/L CHAPTER 13 5.4 × 10−13 17 11.5% Na2 HAsO3 , 3.54 % As2 O5 0.799 V 18 1.47 mL 10 (a) −0.028 V 11 (a) 1.353 V (b) 0.639 V (c) 0.84 V 19 3.8 × 10−3 M (b) 0.034 12 3PVF + AuCl4 − = 3PVF+ + Au + Cl− , K = 6.9 × 1070 (b) −0.020 V 13 (a) 0.845 V (c) −0.497 V 14 0.446 V 15 (a) × 10−4 % (b) 0.084 V CHAPTER 15 7.7 × 10−5 M 10 [Fe3+ ]/[Fe2+ ] = : (c) 0.261 V 11 c 16 −0.505 V 17 (a) 0.02 pH unit, 1.2 mV, 4.8% (b) 0.002 pH unit, 0.12 mV, 0.48% 18 (a) 5.78 (b) 10.14 (c) 12.32 (d) 13.89 CHAPTER 16 29 0.25 μ m, 250 nm 20 11.2 30 7.5 × 1014 Hz, 25, 000 cm−1 ˚ 5, 000 − 670 cm−1 31 20, 000 − 150, 000 A; 21 0.015 M 32 9.5 × 104 cal einstein−1 19 (a) −0.419 V (b) −0.472 V (d) −0.524 V 33 0.70 A, 0.10 A, 0.56 T, 0.10 T 22 0.0079 M −4 23 4.8 × 10 M 34 20 24 (a) 0.16) (b) 18.9 mV 35 4.25 × 103 cm−1 mol−1 L 25 0.020 36 (a) 0.492 (b) 67.8% 26 9.5 × 10 37 5.15 × 10 cm−1 mol−1 L 27 1.07 × 104 38 1.25 −4 39 0.528 g CHAPTER 14 40 79.0% (a) IO3 − + 5I− + 6H+ = 3I2 + 3H2 O (b) 4Se2 Cl2 + 6H2 O = 2H2 SeO3 + 6Se + 8Cl− + 8H+ (c) H3 PO3 + 2HgCl2 + H2 O = H3 PO4 + Hg2 Cl2 + 2H+ + 2Cl− (a) 3MnO4 2− + 2H2 O = MnO2 + 2MnO4 − + 4OH− (b) 2MnO4 − + 5H2 S + 6H+ = 2Mn2+ + 5S + 8H2 O (c) 2SbH3 + 4Cl2 O + 3H2 O = H4 Sb2 O7 + 8Cl− + 8H+ (d) FeS + 3NO3 − + 6H+ = Fe3+ + S + 3NO2 + 3H2 O (e) 8Al + 3NO3 − + 5OH− + 2H2 O = 8AlO2 − + 3NH3 (f) 5FeAsS + 14ClO2 + 12H2 O = 5Fe3+ + 5AsO4 3− + 5SO4 2− + 14Cl− + 24H+ (g) 5K2 NaCo(NO2 )6 + 12MnO4 − + 36H+ = 10K+ + 5Na+ + 5Co3+ + 30NO3 − + 12Mn2+ + 18H2 O 41 (a) 0.152 g/L (b) 0.193 g/day 42 0.054 mg 43 0.405 ppm N 44 1.593 45 4.62 mg/L, 2.61 mg/L 46 0.332% Ti, 1.62% V 48 (a) 1.3 × 10−7 M (b) 200 50 (b) slope = εb2 as c → and εb1 as c → ∞ 51 (a) 256 nm (b) Deuterium or xenon-arc LEDs also available (c) Quartz or fused silica cells CHAPTER 17 10 0.715 V, 0.771 V, 1.35 V, 1.46 V 24 1.5 ppm per 0.0044 A 11 0.360 V 12 E = [(1)E0 Fe3+ , Fe2+ + (2)E0 Sn4+ ,Sn2+ ]/[(1) + (2)] 13 E = (nFe E0 Fe3+ ,Fe2+ + nMn E0 MeO4− ,Mn2+ )/(nFe + nMn ) − [(8)(0.059)/(nFe + nMn )]pH, 1.33 V (for pH 0.68) 14 (a) 0.319 V, −0.780 V, 1.6 × 1012 2.6 × 1022 15 8.9 ppm (b) 0.691 V, −0.154 V, (c) 120 49 551 nm 1.127 V 0.735 V, 0.771 V, 1.218 V, 1.28 V (c) 0.25 25 13% 26 4.5 × 10−9 % 27 190 ppm 28 5.9 ppm 29 84 ppm 30 79 M&Ms in the bag Christian7e a06.tex V2 - 08/13/2013 8:54 A.M Page 814 ANSWERS TO PROBLEMS 814 98 κ = 6.37 × 103 cm−1 CHAPTER 18 12 D = KD (1 + 2Kp KD [HBz]a )/(1 + Ka /[H+ ]a ) 13 8.0 14 48% 15 95% 99 G = 23.5 nS 103 pH 9.00: μeo = 2.3 × 10−8 m2 /V s Net flow is towards the negative electrode pH 3.00, μeo = −2.0 × 10−8 m2 /V s Net flow is towards the positive electrode 16 0.016 M 104 Rs = 28 17 96.2% extracted with 10 mL; 99.45% extracted with × mL 106 5.1 18 2.7% 19 (a) 1.3 × 10−7 (b) 200 107 0.119 mM 109 35.22, 34.92, 32.41 ng/mL (c) 123 CHAPTER 22 CHAPTER 19 0.041 cm/plate 16 217.07017 Da 1.06 × 10 cm 17 [M − H]− , m/z 155 = 100%; M + 1, m/z 156 = 7.7%; M + 2, m/z 157 = 33% 10 mL/min, N, H: 120.2, 2420, 0.123; 90.3, 2500, 0.120; 71.8, 2550, 0.118; 62.7, 2380, 0.126, 50.2, 2230, 0.135; 39.9, 1830, 0.164; 31.7, 1640, 0.183 Optimum near 75 mL/min 11 Rs = 0.96 Not quite resolved 18 R = 69, 692 19 RFWHM = 10, 665 20 R = 34 21 −2.03 ppm CHAPTER 20 22 v = 6.67 × 105 m s−1 23 14 ns 10 2810 torr inlet pressure 11 20.9 ppm CHAPTER 23 CHAPTER 21 80 (a) 2058 plates (b) 0.014 cm (c) 1.09 (d) 57 cm (e) tRA = 29.86 min; tRB = 32.56 81 270 mmol/L 12 48.5 s 13 38 min; 19 min, 3.4 14 12.7 h 82 6.7 g resin 83 (a) HCl (b) H2 SO4 11 33.2 min, 66.5 (c) HClO4 (d) H2 SO4 86 Hz 87 61 μg/mL 15 132 h 16 3.82% 17 Km = 1.20 ± 0.05 mM 88 277.5 nm 90 120 nL; CCl /CIO3 = 0.53 CHAPTER 26 91 CCl /CIO3 = 0.25 3.3 × 10−6 g/Lair 94 MeOH : H2 O: 141 psi; acetronitrile : H2 O: 73.5 psi 380 ppt 95 For 0.02 μM LiOH, 54.4 S/cm; For H2 O, 54,8 nS/cm 96 149.85 μS/cm 97 (a) DK+ = 1.95 × 10−9 m2 s−1 ; DCl− = 2.03 × 10−9 m2 s−1 (b) rK+ = 0.125 nm; rCl− = 0.120 nm CHAPTER G 16 ATTGCATTCCGTA Christian7e bindex.tex V1 - 08/21/2013 12:29 A.M Page 815 Index Pages preceded by a letter are for text website materials: C Clinical chemistry, Chapter 25 E Experiments EN Environmental, Chapter 26 G Genomics, Chapter G P Periodic table, Appendix E S Safety, Appendix D A Absolute cell reference, 114 video, 115 Absolute error, 71 Absolute method, 13 Absolute uncertainty, 66 Absorbance, 495 optimal range, 526 Absorbance calibration, 518 Absorbance ratio plotting, 682 Absorption spectrum mechanism, 531 Absorptivity, 496 Accelerated solvent extraction, 585 Accuracy, 62 relative, 71 in validation, 137 Acid concentrations, inside back cover Acid-base concepts, 222 Acid-base equilibria in water, 225 Acid-base reactions in different solvents, 224 Acid-base theories, 223 Acid-base titration experiment, E12 Acid-base titrations, amino acids, 309 polyprotic acid, 310 strong acid, 282 weak acid, 290 weak base, 295 Acidic solution, 229 Acidosis, 261 Activated complex, 772 Activation overpotential, 470 Activity, 212 enzyme, 774 Activity coefficient, 212 in dilute solution, 212 calculation of, 213 properties of, 216 nonelectrolytes, 217 neutral species, 217 Adenine, G3 Adsorption chromatography, 604 Adsorption indicators, table of, 380 Affinity chromatography, 654 Air analysis sampling train, EN4 Air monitoring, 642 Air sample analysis, EN7 Air sample bags, EN7 Air sample collection, EN2 aerosol constituents, EN6 sample size, EN3 Air sampling devices, EN6 Air sampling pumps, EN5 Albumin determination, C6 Aliquot, 31 Alkali reserve, 261 Alkaline solution, 229 Alpha(α)-values, 248 log-concentration diagram from, 276 Chapter website Amino acids, thin-layer chromatography separation, E67 titration, 309 Ammonia buffer pH 10 solution, E20 Amperometric electrode, enzymatic, 473 oxygen, 472 Amphoteric, 691 Amphoteric salts, 255 Analgesics, HPLC determination, E71 Analysis sample, Analysis variance, 111 Analyte, 8, 16 Analytical balance, 23 electronic, 25 micro, 26 semimicro, 26 use of, E1 Analytical chemistry history, Analytical chemistry journals, 794 Analytical concentration, 156, 195, 248 Analytical methodology, hierarchy of, 144 Analytical methods, comparison of, 13 Analytical process, defining the problem, Analytical results, expressions of, 159 Analytical science, definition, Analyze, 16 Angstrom, 214 Anion exchange resins, 659 separation of metal ions, 660 Anode, 385 Anodic current, 469 Antibody, C7 monoclonal, C10 Antibonding orbital, 485 Anticoagulant, 9, C3 Antigen, C7, C8 Antigen-antibody complex, C7 affinity, C8 avidity, C8 Antimony, iodine titration, E34 Anti-serum, C7 APC tablets, UV analysis, E54 Archimede’s principal, 26 Argon ionization (β-ray) detector, 633 Array spectrometer, 522 Arrhenius, Svante, 223 Arrhenius theory, 223 acid, 223 base, 223 Ascarite, 42 53 Aspirin, back titration of, E17 HPLC determination, E71 standard solution, E71 UV determination, E54 Asymmetry potential, 414, 416 Atomic absorption spectrometry, 556 background correction, 564 ionization interference, 566 light sources, 558 spectral interferences, 564 Atomic emission spectrometry, 569 Atomic fluorescence spectrometry, 549, 574 Atomic spectrometry, 572 physical interferences, 567 sample preparation, 567 Atomic weight, 149 Atomic weights, inside front cover ATR, 548 Attenuated total reflectance, 525 Autocatalytic decomposition, 452 Automated devices, 785 815 Christian7e bindex.tex INDEX 816 Automated instruments,775 Automatic devices, 784 Automatic instruments, 787 Automatic titrator, 463, 785 Automation, 784 Autoprotolysis, 226 Autoprotolysis constant, 226 Auxiliary electrode, 467 Auxochrome, 485 Average linear velocity, 610 Avogadro’s number, 150, 151 proposed change, 150 B BAC, G7 Back extraction, 585, 586 Background electrolyte, 711 Back titration, 177 of aspirin, E16 Bacterial artificial chromosome, G7 Balance, see Analytical balance Balancing redox reactions, 437 Balometer, 517 0–0 Band, 531 Band broadening, 607 Bandpass, 518 Bandwidth, 518 Base concentrations, inside back cover Base peak, 737 Baseline method, 503 Bases, conjugate acids, 234 Basic solution, 229 Batch instruments, 788 Bates, Roger, 419 Bates-Guggenheim convention, 419 Bathochromic shift, 486 Beckman, Arnold, 409 Beer’s law deviations, chemical, 527 instrumental, 529 Beer’s law, 494 and mixtures, 498 Beta(β)-values, 336 BGE, see Background electrolyte Bicarbonate in blood, titration of, E18 Biogel, 653 Biohazard hood, 45 Bioluminescence, 539 Biot’s law, 685 Biuret rection, 488 Blank, 11 Blank solution, 520 Blood collection, C3 Blood composition, C2 normal ranges of constituents, C2 Blood glucose determination, C4 Blood pH, 231 measurement of, 442 standard buffer for, 420 Blood plasma, 10, C2 Blood serum, 9, C2 Blood urea nitrogen determination, C4 Boosted discharge hollow cathode lamp, 575 Boosted HCLs, 559 V1 - 08/21/2013 12:29 A.M Page 816 Boundary potential, 416 Boyle, Robert, Breathalyzer, 491 Bromcresol green solution, E15 Bromthymol blue, 288 Brønsted acid, salt of weak base, 236 Brønsted base, salt of weak acid, 234, 236 Brønsted-Lowry theory, acid, 224 base, 224 Buffer, composition, 238 definition, 238 Buffer calculations, 238 polyprotic acids, 245 Buffer capacity, 307 Buffer index, 240 Buffer intensity, 240, 292 derivation of, supplement 8.11 website program for, 307 Buffer region, 292 Buffering capacity, 240 maximum, 243 total, 292 Buffering intensity, maximum, 241 Buffering mechanism, 240 Buffers (see also Standard buffers), biological, 263 clinical, 263 Good, 265 phosphate, 245, 263 physiological, 261 Tris, 264 Bunsen, Robert 548 Buret, 35 calibration of, 40 use of, E2 Burners for flame spectrometry, 554 C Caffeine UV, determination, E54 Calcium, atomic absorption determination, E57 EDTA titration in blood, 336 standard solution, E58 Calcium-selective electrode, 425 Calgamite indicator, 335 Calibration curve, 13 calculation of unknown with spreadsheet, 502 potentiometric, 411 spreadsheet plotting of, 117 Calibration of glassware, 37 Calomel electrode, 402 Capacity factor, 609 Capillary column manufacturers, 626 Capillary electrochromatography, 725 Capillary electrophoresis, 708, 711 detectors, 715 injection modes, 712 micro-chip, 723 plate numbers, 721 resolution, 721 separation efficiency, 716 Capillary gel electrophoresis, 708 Capillary isoelectric focusing, 710 Capillary zone electrophoresis, 708 Carbon dioxide removal, 697 Carbon electrode, 471 Carrier gas, 620, 621 Catalyst, 193, 771 Catalytic combustion detector, 632 Catalytic electrode, 473 Cathode, 385 Cathodic current, 469 Cation exchange resins, 381, 659 CCD, see Charge coupled device CD, see Cyclodextrin CE, see Capillary electrophoresis Cell constant, 677 Cell potential, 385 Cell voltage, 388 and reaction tendency, 392 Cell without liquid junction, 404 Cell without transference, 404 Cerium (IV) primary standard, 453 Certified standards, 15 CF, see Cyclofructan 21 CFR, Part 11, 145 Characteristic of logarithm, 70, 798 Charge balance equations, 205 Charge balance method, Excel for acid-base titration, 285 pH of phosphoric acid, 253 Charge concentration, 205 Charge transfer transition, 489 Charge-coupled device, 516 Chelate effect, 326 Chelate, 325 light absorption mechanism, 489 solvent extraction, 336 Chelating agent, 168, 325 gravimetric precipitate, 354 Chelometric titration, 325 Chelon effect, 326 Chemical abstracts, 794 Chemical literature, Chemically modified electrode, 472 Chemiluminescence, 538 Chiral chromatography, 654 Chiral compounds, separation of, 644 Chiral stationary phases, 663 Chloride, Fajan determination, E23 FIA determination, E79 gravimetric determination of, E6 potentiometric titration, E40 spectrophotometric determination, E79 standard solution, E79 Chlorofluorocarbon determination, EN8 Chromatogram, 604 Chromatographic separations, principles of, 603 Chromatographic technique types, 604 Chromatography nomenclature, 605 Chromatography resolution, 615 Chromatography terms, 606 Chromatography, adsorption, 604 column efficiency, 607 (see also Column efficiency) ion exchange, 605 IUPAC definition, 597 Christian7e bindex.tex V1 - 08/21/2013 12:29 A.M Page 817 INDEX meaning, 597 normal-phase, 605 numerical simulation, 600 partition, 605 resolution equation, 615 reversed-phase, 605 simulation software, 616 size exclusion, 605 types, 597 Chromium, spectrophotometric determination, E50 standard solution E51 Chromogen, 485 Chromophore, 485 conjugated, 487 Chromosomes, G1 Chromosorb P, W, 620, 623 Circular dichroism, 685 Clausius, Rudolf Julius Emanuel, 192 Clinical chemistry, C1 common determinations, C4 CME, 472 Codon, G14 Coefficient of determination, 105 spreadsheet calculation, 118 Coefficient of variation, 74 Coenzyme, 774 Cold vapor AAS, 549 Cold vapor generation, 563 Colloidal particles, 346 Color, complementary, 478, 481 Column bleed, and GC-MS, 628, 745 Column efficiency, and particle size, 614 Combination absorption bands, 491 Combination pH electrode, 415 COMERRR, 145 Common ion effect, 203 Complementary color, 478, 481 Complex, 194 Concentration, analytical, 156, 195, 248 charge, 205 effective, 212 equilibrium, 156, 195, 248 from electrode potential, 411 volume/volume for gases, EN2 Concentration sensitive detectors, 637 Confidence interval, 84 Confidence level, 84 Confidence limit, 75, 84 using the range, 99 Conjugate pair, 224 Conjugated chromophore, 487 Continuous analyzers, 786 Continuum source AAS, 563 Control charts, in quality assurance, 143 Control limits, 83 Control sample, 15 Control-loop, 786 Copper, iodometric determination, E32 Coprecipitation, 347 Correlation coefficient, 104 Cotton effect, 685 Countercurrent extraction, 598 Craig, Lyman C., 600 Critical micelle concentration, 725 817 Crosslinking of resins, 659 Crown ether, 427 Crucible holder, 46 Crucible, Gooch, 46 porcelain filter, 46 sintered glass, 46 CSP, see Chiral stationary phase Current, anodic, 469 cathodic, 469 Current-voltage curve, 468 Cyclodextrins, 644, 664 Cyclofructans, 664 Cytosine, G3 CZE, see Capillary zone electrophoresis D Dalton, 150 Dark current, 513 Dark response, 520 Data analysis regression, video, 87 Davies equation, 215 Davy, Humphry, 222 Dead time, 786 Deaeration, 471 Debye, Peter J W., 213 Debye-Hăuckel equation, 213 Davies modification, 215 Extended, 213 Decomposition potential, 468 Defining the analytical problem, Degeneracies, 550 Degrees of freedom, 72 pooled standard deviation, 90 Dehydrite, 53 Dehydrogenase reactions, 779 Denatured protein, 773 Density, 155 of air, 26 Deoxyribonucleic acid, G3 (see also DNA) Depolarized electrode, 469 Depolarizer, 469 Derivative titration curves, program for,304 Derivative titration, 458 Desiccator, 43 vacuum, 43 Detection limit, 105 Determinate error, 63, 75 (see also Systematic error) Determine, 16 Deviation factor, 99 Dichlorofluorescein solution, E23 Dideoxynucleotides, G8 Diffraction grating, 506 dispersion, 508 resolving power, 508 Diffraction grating equation, 507 Diffraction order, 507 Diffusion layer, 469 Diffusion potential, 416 Digestion of precipitates, 345 Dihydrogen phosphate pH, 256 Dilution calculations, 156 Dimensional analysis, 153 Dipole moment, 489 Discrete analyzers, 787 Dissociation constant, 323 Dissociation constants for acids, 801 Dissociation constants for bases, 802 Dissolving samples, 52 inorganic solids, 52 Distribution coefficient, 579 Distribution ratio, 580 Dithizone, 336, 584 Diverse ion effect, 217 on acids and bases, 266 Diverse salt effect, 212 DME, 471 DNA, G3 (see also Deoxyribonucleic acid) DNA annealing, G6 DNA chips, G-12 DNA hybridization, G6 DNA microarrays, G-12 DNA oligonucleotide, G3 DNA polymerase, G6 DNA replication, G6 DNA sequencing, G8 Donnan potential, 654 Double-antibody technique, C10 Draft genome, G13 Dropping mercury electrode, 471 Drude’s equation, 685 Dry ashing, 11, 52 Dry electrolytic detector, 636 Drying agents, 44 Drying oven, 45 Drying samples, 51 Dry-test meter, EN4 E Eddy diffusion, 610 EDTA, 325 ladder diagram 327 pH, 260 primary standard, 335 standard solution, E20 titration curves, 331 EDTA complexes, formation constants of, 805 EDTA equilibria, 326 pH effect, 328 Effective concentration, 212 e-folding time, 672 EGTA, 349 Einstein relation, 677 Electrical conductance, 677 Electrical mobility, 676 Electrocatalyst, 473 Electrochemical cell, 384 (see also Voltaic cell) Electrochemical sensor, 472 Electrode, ultramicro, 474 Electrode offset, 441 Electrode potential, 385 limitations, 395 measuring, 385 Electrodeless discharge lamp, 559 Electrolytic cell, 384 Electromagnetic radiation, 479 absorption of, 480 Electromagnetic spectrum, 479 Christian7e bindex.tex INDEX 818 Electrometer, 409 Electron capture detector, 634 Electron multiplier, 746 Electroneutrality principle, 205 Electronic balance, 25 use of, E1 Electronic notebook, 23 Electronic records, 145 Electronic signatures, 145 Electronic transition, 481, 482 kinds of, 485 Electroosmotic flow, 711, 717 Electrophoresis, 708 (see also Capillary electrophoresis) Electrophoretic mobility, 719 Electrostacking, 714 Electrostatic precipitator, EN6 Electrothermal AAS, 549 Electrothermal atomization, 561 Electrothermal atomizer, detection limits, 563 ELISA, C11 Emission filter, 535 End point, 35, 167, 282, 288 End-capping, 655 Endonuclease, G5 Enthalpy, 191, 326 standard, 191 Entropy, 191, 326 standard, 191 Enzymatic analysis examples, 779 Enzyme activity, 774 Enzyme determinations, 781 Enzyme electrode, amperometric, 473 Enzyme immunoassay, C11 Enzyme inhibitor determination, 782 Enzyme inhibitors, 774 Enzyme kinetics, 772 pseudo first-order, 773 Enzyme nomenclature, 776 Enzyme specificity, 776 Enzyme substrate determination, 777 Enzyme-linked immunosorbent assay, C11 Enzymes, 772 competitive inhibitors, 774 determination of, 777 molecular activity, 774 noncompetitive inhibition, 774 properties of, 802 specific activity, 774 substrate inhibition, 774 EOF, see Electroosmotic flow EPA performance-based analysis, EN13 Equilibria, concentration effects, 193 heterogeneous, 211 pressure effects, 192 types, 190 Equilibrium calculations, approximation approach steps, 207 chemical reactions, 195 dissociating species, 201 Goal Seek, 198, 204 simplifying assumptions, 200 systematic approach steps, 207 Equilibrium concentration, 156, 195, 248 Equilibrium constant, V1 - 08/21/2013 12:29 A.M Page 818 acid, 225 concentration, 217 and Gibbs free energy, 191 molar, 189, 227 redox reaction calculation, 438 temperature effects, 192 thermodynamic, 217 Equilibrium constants, precipitates, 194 stepwise, 194 strong electrolytes, 194 weak electrolytes, 194 Equilibrium potential, 391 Equivalence point potential, 440 Equivalence point, 167, 282 Equivalent conductance at infinite dilution, 677 Equivalent weight, 154, text website Chp5 in clinical chemistry, 154 Eriochrome Black T, 334 Eriochrome BlackT solution, E20 Error, 75 (see also Propagation of errors) absolute, 71 mean, 71 relative, 71 types of, 15 Error bars, video, 102 Erythrocytes, C1 Ethylenediaminetetraacetic acid, 325 (see also EDTA) Evanescent wave, 541 Excel Solver, see Solver Excel, see Spreadsheets, Videos Exchange capacity of resin, 659 Excitation filter, 535 Excited state, 504 Exclusion limits in gel chromatography, 653 Exonuclease, G5 Exponents, 797 Expression proling, G13 Extended Debye-Hăuckel equation, 213 F F values table, 87 Fab fragment, C7 Fajan determination, E23 Fajan’s method, 380 Faraday cup, 763 Faraday’s scheme, 685 Far-IR region, 480, 482 Fast LC, 701 Fc fragment, C7 Feedback mechanism, 786 Fellget’s advantage, 524 Femto, 159 Ferric alum indicator solution, E21 FIA, see Flow injection analysis Fiber optic sensors, 540 Fiber optics, numerical aperture, 511 Fibrin, Fibrinogen, 9, C1 Filter papers, ashless, 46 types of, 47 Filtration, of precipitates, 348 techniques of, 46 Fingerprint IR region, 490 Fingerprints, fluorescence detection, 538 Firebrick, 620 First derivative titration, for Gran plot, 461 First-order reaction, 770 pseudo, 771 Flame AAS, principles, 557 Flame AAS, 549 Flame atomization, 560 Flame emission spectrometery, 549, 553 Flame ionization detector, 632 Flame photometer, 553 Flame photometry, 549 flames 553 Flame spectrometry burners, 554 Flame thermionic detector, 633 Flow injection analysis, 789 system characterization, E76 Fluorescein indicator, 380 Fluorescence immunoassay, C10 Fluorescence inhibition, 533 Fluorescence instrumentation, 535 Fluorescence quenching, 533 Fluorescence spectrometry, 505 Fluorescence, and chemical structure, 533 and concentration, 534 gated measurements, 537 lifetime measurements, 537 mechanism, 530 phase-resolved, 537 time-resolved, 537 Fluoride, ion-selective electrode determination, E25 standard solution, E26 Fluoride-selective electrode, 425 Fluorometer, 535 Fluorometry, 530 Foley Dorsey equation, 608, 609 Forbidden transition, 491, 532 Formal electrode potentials, 806 Formal potential, 394 Formality, 155 Formation constant, 323 Ca-EDTA, 327 conditional, 329 cumulative, 336 Formation constants of EDTA complexes, 805 Formula weight, 150 Formula weights, inside front cover Fourier transform infrared spectrometer, 523 Fourier transformation, 524 Fourier transform-ion cyclotron resonance (FT-ICR), 761 Franklin and Germann theory, 224 Fraunhofer, Joseph von, 548 Fraunhofer lines, 549 Free energy, standard, 191 Frequency domain spectrum, 524 Frequency, 479 Fresenius, Karl Remigius, Fresnel loss, 527 F-test, 86 video, 88 Christian7e bindex.tex V1 - 08/21/2013 12:29 A.M Page 819 INDEX FTIR, see Fourier transform infrared spectrometer Full spectrum analysis, 522 Full-width half maximum, 505 Fume hood, 45 Fusion, 52 fw, 150 FWHM, 505 G Galvanic cell, see Voltaic cell Gaol Seek, limitation of, 199 Gas adsorption tubes, EN6 Gas analyzer calibration, EN9 Gas chromatography, 619 adsorption, 619 of chiral compounds, 644 compounds determined, 622 high speed, 643 partition, 619 pyrolysis, 642 quantitative measurements, 639 temperature programming, 638 temperature selection, 638 two-dimensional, 645 of volatile organic compounds, 643 Gas chromatography columns, capillary, 624 manufacturers, 626 packed, 623 porous-layer open-tubular (PLOT), 625 support coated open tubular (SCOT), 625 wall-coated open-tubular (WCOT), 624 Gas chromatography detectors, 630 argon ionization (β-ray), 633 atomic emission, 634 catalytic combustion, 632 concentration vs mass flow sensitive, 637 dry electrolytic, 636 electron capture, 634 flame ionization, 632 flame thermionic, 633 Hall electrolytic conductivity, 635 helium ionization, 634 nitrogen-phosphorus, 633 phosphorus, 633 photoionization, 635 pulsed discharge, 634 sulfur, 633 sulfur and nitrogen chemiluminescence, 635 thermal conductivity, 630 vacuum ultraviolet, 637 Gas chromatography experiment, E69 Gas chromatography-mass spectrometry, 622, 741 (see also GC-MS) column bleeding, 745 ionization sources, 741 Gas chromatography stationary phases, 626 carbowax, 626 ionic-liquid, 628 retention indices, 628 selection of, 628 Gas constant, 191 Gaussian curve, 64 819 Gaussian distribution, of analyte in bulk material, 109 Gay-Lussac, Joseph, 378 GC x GC, 619, 623, 645 (see also Two-dimensional chromatography) GC, see Gas chromatography GC-MS, 622 (see also Gas chromatography-mass spectrometry) GC-MS experiment, E72 GC-VUV, 637 Gel filtration chromatography, 653 Gel permeation chromatography, 653 Gene expression profiling, G13 Gene expression, G1 Gene sequencing, G3 Genetic code, G14 Genomic library, G7 Genomics, G13 GF, see Gravimetric factor Gibbs free energy, 191 (see also Free energy and equilibrium constant) Gibbs, J Willard, 191 Gibbs-Stockholm convention, 386 Glass pH electrode, acid error, 418 alkaline error, 416 calibration, 414, E24 high pH (full range), 417 mechanism, 415 principle of, 413 Glassware calibration, E4 Glassware cleaning, 729, E3 Globar, 528 Globulin determination, C6 GLP, see Good laboratory practice Glucose, enzymatic determination, E74 standard solution, E75 Glucose determination, 780 Glucose electrode, 473 Glucose oxidase, 776 Glycolysis, C3 GMP, see Good manufacturing practice Goal seek, charge balance method titration curve, 285, 293 equilibrium calculation, 198 eliminating premature solution, 202 method of charge balance for pH, 253 pH of phosphoric acid, 253 polynomial equation solution, 199 shortcomings and solution, 202 Golay, Marcel J E., 624 Golay equation, 613 Gooch crucible, 46 Good buffers, 265 Good laboratory practice, 133 in TLC, 703 Good manufacturing practice, 145 Grab sample, Grades of chemicals, inside back cover Gradient elution in HPLC, 701 in HPTLC, 706 Gradient elution in HPLC, pumping systems, 668 Gran plot, 459 advantage, 460 from first derivative, 461 volume correction, 460 Graphing, using spreadsheets, 112 Graphite Furnace AAS, 549 Grating, see Diffraction grating Gravimetric analysis, 12 examples, 353 precipitation conditions, 345 precipitation process, 344 steps of, 343 weight relationships, 180 Gravimetric calculations, 349 mixtures, 352 Gravimetric factor, 181, 349 examples, 182 Gross sample, Ground state, 482 Groundwater sampling, EN10 Grubbs test for outliers, 97 Guanine, G3 Guard column, 672 Gylcolyis, prevention, E19 H Hagen-Poiseuille equation, 676 Hair shampoo pH determination, E24 Half-life, 770 second-order reaction, 771 Half-reaction potential, 386, 438 Half-reaction, 386, 438 Half-wave potential, 469 Hall electrolytic conductivity detector, 635 Hamilton syringe cleaning, E69 HCL, see Hollow cathode lamp Headspace analysis, 641 Helium ionization detector, 634 Helmholtz, Hermann L F Von, 717 Helmholtz plane, 717 Hemolysis, C3 Henderson-Hasselbalch equation, 238 thermodynamic equilibrium constant, 266 Heparin, 830, C3 Heptane, GC determination, E69 Heterogeneous equilibria, 211 Hexane, GC determination, E69 High performance liquid chromatography, 651 (see also HPLC) principles of, 651 stationary phases, 654 (see also HPLC stationary phases) subclasses, 652 High performance thin-layer chromatography, 703, 704 gradient elution, 706 High speed gas chromatography, 643 HILIC, see Hydrophilic interaction chromatography Hollow cathode lamp, 558 boosted, 559 boosted discharge, 575 Horseradish peroxidase, 780 HPLC, 651 (see also High performance liquid chromatography) Christian7e bindex.tex INDEX 820 HPLC (continued) gradient elution, 701 open tubular, 702 narrow bore columns, 701 subclasses, 652 two-dimensional, 699 HPLC detectors, aerosol charge, 681 amperometric, 686 capacitive coupled contactless conductivity (C4 D), 681 chemiluminescence, 688 chiral, 685 condensation nucleation light scattering, 681 coulometric, 686 criteria for, 672 electrical conductivity, 676 evaporative light scatter, 779 fluorescence, 684 mulitangle light scattering, 676 photodiode array (PDA), 682 polarimetric, 685 position sensitive, 674 pulsed amperometric, 686 radioactive, 689 refractive index, 673 universal, 673 UV-Visible, 682 viscosity, 676 HPLC equipment, 665 column designs, 670 column oven, 672 detectors, 672 (see also HPLC detectors) guard column, 672 pumps, 667 sample injection system, 669 solvent delivery system, 666 HPLC method development, 700 HPLC-MS (see Liquid chromatography-mass spectrometry) HPLC stationary phases, alumina, 665 high-purity silica, 654 microporous particles, 655 monolithic, 661 perfusion packings, 656 porous graphitic carbon, 665 nonporous packings, 657 superficially porous particles, 657 titania, 665 zirconia, 665 HPTLC, see High performance thin-layer chromatography Huber equation, 613 Hăuckel, Erich, 213 Human Genome Project, G3 Hybridization, G6 Hydride generation, 563 Hydrochloric acid, standardization of, E15 standard solution of, 42 Hydrogen electrode, 403 (see also NHE) Hydrolysis, 234 Hydrolysis constant, salt of weak acid, 235 salt of weak base, 237 V1 - 08/21/2013 12:29 A.M Page 820 Hydronium ion, 225 Hydrophilic interaction chromatography, 653 stationary phases, 663 Hydrophilic, 347 Hydrophobic, 347 8-Hydroxyquinoline, see Oxine Hyperchromic shift, 486 Hyperchromism, 486 Hyperconjugation, 487 Hypochlorite, iodometric titration, E30 Hypochromism, 486 Hypsochromic shift, 486 I IC, see Ion chromatography ICP-MS, 572 (see also Inductively coupled plasma-mass spectrometry) IEC, see Ion exchange chromatography Immunoassay, heterogeneous, C11 homogeneous, C11 principles of, C7 Immunoassay specificity, C9 Immunoglobulins, C7 Immunology, C7 Impactor, EN6 Impedance, high input, 410 Impinger, EN6 Inclusion in precipitates, 347 Indeterminate error, 64 (see also Random error) Indicator electrode, 400, 404 Indicator, 167, 288 (see also pH indicator) adsorption, 378, 380 chelometric, 334 pH transition range, 288 precipitation, 378 Induction coupled plasma, 569 Induction coupled plasma spectrometry, 549, 569 (see also Inductively coupled plasma spectrometry) Induction coupled plasma mass spectrometry, 550 Inductively coupled plasma-mass spectrometry, 753 (see also Induction coupled plasma mass spectrometry) isobaric interferences, 753 Infrared radiation, absorption of, 489 Infrared spectra, 490 quantitative measurements, 503 Ingamell’s sampling constant, 108 Inner-filer effect, 534 Instability constant, 323 Instrument standardization, 13 Instrumental analysis, 12 Intercept, spreadsheet calculation, 118 standard deviation of, 102 Interferogram, 523 Interferometer operation, 523 Interferometer, 505 Internal conversion, 531 Internal standard calibration, 14 Internal standard, in atomic spectrometry, 567 in gas chromatography, 640 isotopically labeled, 747 International unit, 774 Intersystem crossing, 531 Iodide, potentiometric titration, E40 Iodimetry, 447 Iodine solution, standardization, E34 Iodometric calculations, 450 Iodometry, 449 end point detection, 450 potentiometric titration, E40 Ion chromatography, 653, 692 anion, 693 cation, 693 carbon dioxide removal, 697 electrodialytic eluent generation, 697 membrane suppressors, 696 nonsuppressed, 694 suppressor column, 693 Ion chromatography exclusion, 654 Ion cyclotron resonance, 760 Ion detectors, 763 Ion exchange chromatography, 605 of amino acids, 691 Ion exchange chromatography, 652 Ion exchange phases in modern chromatography, 660 Ion exchange resins, 658 anion, 659 cation, 659 gel-type, 658 macroreticular, 659 Ion exclusion chromatography, 654 Ion mobility spectrometry, 762 Ion pair chromatography, 699 Ion size parameter table, 214 Ion size parameter, 214 Ionic mobility, 676 Ionic strength, 212 weak acids, 213 Ionophore, 426 Ion-selective electrodes, advantages and disadvantages, 431 glass membrane, 424 liquid-liquid, 425 measurements with, 430 mechanism of response, 427 plastic membrane-ionophore, 426 potential of, 427 selectivity coefficient, 428 selectivity coefficient determination, 430 sensitivity of, 430 solid-state, 424 in titrations, 458 IR absorption requirement, 489 IR absorption, and molecular structure, 489 iR drop, 467 IR region, 480 Iron, dichromate titration, E27 spectrophotometric determination, E41, E43 standard solution, E42 Irreversible reaction, 398, 447 Irreversible reduction/oxidation, 470 Isoelectric focusing, 710, G15 Christian7e bindex.tex INDEX Isoelectric point, 691 Isoenzyme, 781 Isomorphous replacement, 347 Isopotential point, 421 Isosbestic point, 526 Isotachophoresis, 726 Isotopes, relative abundances, 737 J Jacquinot’s advantage, 524 Johnson noise, 526 Joule heating, 719 K Kelvin, Lord, Kinetics, 769 of enzyme reactions, 772 Kirchoff, Gustav 548 Kjeldahl, Johan, 310 Kjeldahl analysis, 310 micro, 312 Kjeldahl digestion, 54 Kjeldahl flask, 57 Knox equation, 613 Kovats retention index, 628 L Laboratory information management systems (LIMs), 792 Laboratory materials, properties, 23 Laboratory notebook, 20 documentation of, 22 electronic, 23 Laboratory safety, 57, S1 Laboratory sample, Lactic acid dehydrogenase, 779 Ladder diagram, EDTA 327 Ladder diagrams, 247 Laminar flow, 716 Laminar-flow hood, 45 Laser ablation ICP, 573 Laser induced fluorescence, 685 Lavoisier, Antoine, Law of mass action, 188 LC-MS (see Liquid chromatography-mass spectrometry) LCW, fluorescence detector, 535 LCW, see Liquid core waveguide Le Chˆatelier, Henry-Louise, 192 Le Chˆatelier’s principle, 192, 193, 203 Lead, spectrophotometric determination, E47 standard solution, E47 Lead poisoning treatment with EDTA, 336 Least-squares line, significant figures, 120 Least-squares plots, 100 Leukocytes, C1 Lewis, Gilbert N., 225 Lewis theory, acid, 225 base, 225 Ligand, 323 bidentate, 325 V1 - 08/21/2013 12:29 A.M Page 821 821 Limit of detection, 105 in validation, 139 Limit of quantitation, 106 in validation, 139 Limiting current, 469 Limiting equivalent conductance, 677 Limiting molar conductivity, 679 LIMs, 792 Linear least squares, 99 (see also Least squares) Linearity, in validation, 136 LINEST Excel statistical programs, 120 LINEST, video, 120 Lineweaver-Burk equation, 774 Liquid chromatography-mass spectrometry, 242, 746 ionization sources, 741 of proteins, 747 Liquid core waveguide, 511, 684 Liquid junction, 405 Liquid-junction potential, 405 pH effect, 407 minimizing, 406 residual, 411 temperature effect, 420 Liquid-phase microextraction, 592 Literature of analytical chemistry, 794 Logarithmic concentration diagram, 266 acetic acid, 7.16.2 website from alpha-values, 267, Chapter website ammonium acetate, 269 phosphoric acid, 7.16.3 website spreadsheet construction, 267 system point, 7.16.2 website Logarithms, 797 characteristic, 70, 798 mantissa, 70, 798 significant figures, 70 logC-pH diagrams, master spreadsheet, 267 Longitudinal diffusion, 610 Lovelock, James E., 634 Lowry, Thomas, 224 Low-temperature ashing, 53 L’vov, Boris, 562 M MADI, 750 MALDI-TOF, G15 Manganese, spectrophotometric determination, E50, E52 standard solution, E50 Mantissa of logarithm, 70, 798 Martin, Archer J.P., 597 Masking agent,322 Mass action law, 188 Mass analyzers, 753 Mass balance equations, 204 multiple equilibria, 368 Mass flow sensitive detectors, 637 Mass spectrometry imaging, 752 Mass spectrometry, atmospheric pressure chemical ionization, 746, 748 atmospheric pressure ionization, 746 atmospheric pressure photoionization, 746, 749 base peak, 737 chemical ionization, 744 desorption analysis in real time (DART), 749 desorption electrospray ionization, (DESI) 749 desorption/ionization (NALDI), 751 double-focusing sector, 756 electron ionization, 741 electrospray ionization, 746 elemental formula determination, 740 inlet types, 741 ion cyclotron resonance, 760 ion trap mass analyzer, 757 ionization sources, 740, 741 (see also specific sources) laser desorption/ionization, 750 mass accuracy, 738 mass analyzers, 753 matrix-assisted laser desorption/ionization (MALDI), 750, G15 molecular ion, 742 MS/MS, 765 nanoparticle-assisted laser desorption/ionization (NALDI), 751 negative chemical ionization, 745 nitrogen rule, 740 parent ion, 742 principles, 735 quadrupole mass analyzer, 756 resolution, 737 rule of 13, 740 secondary ion, 752 tandem, 765 time-of-flight analyzer, 758 types of masses in, 736 unit resolution, 738 Mass spectrum, 737 Mass transfer term, 611 Mass, 24 Material safety data sheets, 58 Matrix, 136 Matrix-assisted laser desorption ionization (MALDI), 750, G15 Matrix effect, 136 Maxwell-Boltzmann distribution, 550 McReynolds constants, 629 Mean error, 71 Mean free path, 740, 754 Mechanical slit width, 518 Median, 97 efficiency of, 98 MEKC, 724 Meniscus, 30 Messenger ribonucleic acid (mRNA), G13 Metallic reductors, 476 Method of standard additions, see Standard additions Method of successive approximations, 199 Method validation, 134 Method validation experiment, E82 Methyl purple solution, E39 Methyl red solution, E36 Methyl red, solid-phase extraction of, E61 Micellar electrokinetic chromatography, 724 Michaelis constant, 774 Microbalance, 26 Christian7e bindex.tex INDEX 822 Microburet construction, E37 Microextraction, 590 Microliter, 159 Microplate reader, determination of manganese in steel, E52 spectrophotometric determination of iron, E43 volumetric measurements, E4 Microscale titration, E36 Microsoft Excel, see Spreadsheets Microsoft Excel, see Videos Microtiter plates for SPE, 589 Microwave digestion, 55 Microwave ovens, laboratory, 56 Microwave region, 482 Microwave-assisted extraction, 585 Migration current, 470 Millequivalent, 165 Milliequivalents, text websiteChp5 Milligram percent, 161 Milligrams per deciliter (mg/dL), 162 Millimole, 151 Minimum number of measurements, for a given error, 85 Mixed potential, 412 Modified methyl orange, 298, E15 Mohr method, 378 Molal, 155 Molality, 155 Molar, 152 Molar absorptivity, 496 Molar concentration, 226 Molar mass, 150 Molarity, 152 Molarity calculations, useful rules, 170 Mole, 150 Molecular absorption background in AAS, 549 Molecular activity, 774 Molecular diffusion, 610 Molecular ion, 742 Molecular sieve, 626 Molecular weight, 150 (see also Formula weight) Molecular weight distribution of polymers, 653 Molybenum blue, E49 Monochromator, 504 Monoclonal antibody, C10 Monohydrogen phosphate pH, 257 Monolithic columns, 661 Mother liquor, 345 MSDS, see Material safety data sheets MS/MS, 765 Muffle furnace, 44 Mull technique, 510 Multichannel analyzers, 788 Multiplex advantage, 524 Multiplicity, 530 Multiwalled carbon nanotubes, 471 Mutarotation, 777 MW, 150 MWCNTs, 471 N Nano LC, 670 Nanogram, 159 Nanoliter, 159 V1 - 08/21/2013 12:29 A.M Page 822 Near-infrared (see also NIR), 492 Near-infrared spectrometry, calibration, 492 nondestructive testing, 491 uses of, 492 Near-IR region, 480 Near-IR spectrometer, 525 Near-UV region, 480 Neat sample, 492, 509 Negative pH, 229 Nernst equation, 390 Nernst-Einstein equation, 679 Nersnt glower, 505 Neutral solution, 229 at elevated temperatures, 231 Neutralization reaction, 282 Newton, Isaac, 478 NHE, 386 Nickel, gravimetric determination, E11 Nikolsky equation, 429 limitations of, 430 NIR (see also Near infrared), 492 NIR region, 492 Nitrate, spectrophotometric determination, E46 standard solution, E46 Nitric acid NO2 -free, E21 Nitrogen dioxide determination, EN8 Nitrogen rule, 740 Nitrogen-phosphorus GC detector, 633 Nitrous oxide-acetylene flame, 566 Nominal wavelength, 517 Nondestructive testing by NIR, 491 Normal, 154, text websiteChp5 Normal distribution, 64 Normal error curve experiment, volumetric measurement, E4 Normal hydrogen electrode, 386 Normal phase chromatography, 652 aqueous, 653 Normality, 154, text website Chp5 Normality calculations, text website Chp5 Normal-phase chromatography, 605 Notch filter, 508 Nuclease enzyme, G5 Nucleation, 344 Nucleotide, G3 Nujol, 510 Numerical aperture, 511 O Occlusion in precipitates, 347 Offset of pH electrode, 421 Ohm’s law, 467, 468 Oligonucleotide, G3 Open tubular liquid chromatography, 702 Open-tubular columns, 624 Optical filter, 508 Optical rotary dispersion, 685 Orthophosphate buffers, 245 Ostwald ripening, 345 Ostwald, Wilhelm, Overtone absorption, 491 Oxidation, 383 Oxidizing agent, 384 Oxine, 349 Oxygen electrode, 472 Oxygen removal, 471 Ozone determination, EN8 P PAGE, 709 2-D PAGE, G15 Paired t-test, 93 Parabola mass spectrograph, 755 Parallax error, 35 Parent ion, 742 Partition chromatography, 605 Parts per billion, 160 Parts per million, 160 Parts per thousand, 160 Parts per thousand, 71 Parts per trillion, 160 PBMS, EN13 PCR, see Polymerase chain reaction p-Diphenylamine sulfonate solution, E27 Pearson correlation coefficient, 104 Pentane, GC determination, E69 Peptide, G14 Peptization, 346, 348 Perchloric acid, precautions with, 54 Performance-based measurement system, EN13 Periodic tables on the Web, P1 Permeation tube, EN9 Peroxide, iodometric titration, E30 Pesticide determination, EN13 PFF, see Protein-free filtrate pH calculator for mixtures, 269 pH calculators, 269 pH electrode, see Glass pH electrode pH indicators, inside back cover pH measurement, accuracy, 420 of blood, 422 in nonaqueous solvents, 423 temperature compensation, 422 of unbuffered solution, 422 pH meter, 409 digital, 421 high resolution, 422 operation of, 421 pH scale, 227 pH titration, 457 pH, blood, 231 definition, 228 determination in shampoo, E24 at elevated temperatures, 231 negative, 229 operational definitions, 418 of phosphoric acid, 246 salts of weak acids and bases, 234 of seawater, 272 weak acids, 232 weak bases, 232 pH-stat, 785 pH using Goal Seek, 253 Phenacetin, UV determination, E54 Phenol red solution, E18 Phenoldisulfonic acid solution, E46 Christian7e bindex.tex V1 - 08/21/2013 12:29 A.M Page 823 INDEX Phenolphthalein, 289 Phenolphthalein solution, E13, E39 Phenolsulfonphthalein solution, E18 Phosphate buffers, 245, 263 Phosphate pH, 257 Phosphate, FIA determination, E80 spectrophotometric determination, E80 Phosphorescence, 532 gated measurements, 537 Phosphoric acid, alpha values, 248 ionization of, 245 pH, 246 Phosphorus, GC detector, 633 standard solution, 49 Phosphorous in serum, spectrophotometric determination, E48 Photoionization detector, 635 Photomultiplier tube, 513 Photon detector, 517 Photon energy, 480 Phototube, 513 Phrap, G11 Phred, G11 Physiological buffers, 261 pI, 691 Pico, 159 Pipet, 31 calibration of, 40 graduated, 31 measuring, 31 syringe, 32 transfer, 31 use of, E2 volumetric, 31 Pipetting procedure, E3 Pipettor calibration, E4 Pirkle phases, 663 Planar gel electrophoresis, quantitation, 710 Planck’s constant, 480 Plasma, 10 Plasmids, G7 Plate height, 607 effective, 609 for HPLC column, 613 reduced, 612 Plate number, 607 (see also Theoretical plate) effective, 608, 614 for skewed peaks, 608 Platelets, C1 Platinum black, 386, 403 PLOT columns, 625 Plotting in Excel, video, 102, 118 pOH, 228 Point-of-care analysis, C6 Poising capacity, 412 Poisson distribution, 109 Polarography, 473 Polyacrylamide gel electrophoresis (PAGE), 709 Polyacrylamide gel electrophoresis (see 2-D PAGE) Polymerase chain reaction, G6 Polynomial equation, Goal Seek solution, 198 Polyprotic acids, 823 buffer calculations, 245 salts of, 255 species distribution, 248 titration, 300 Pooled standard deviation, 89 Portable GCs, 643 Post-column reaction detection in HPLC, 689 Postprecipitation, 348 Potassium dichromate, primary standard, 453 standard solution, E28 Potassium iodate standard solution, E30 Potassium ion, standard activity solutions, 430 Potassium permanganate solution, E36 standardization, E37 Potassium thiocyanate standardization, E22 Potassium-selective electrode, 426 Potential measurement cell, 410 Potential, complexation dependence, 395 at equivalence point, 440 measurement of, 409 mixed, 412 pH dependence, 395 Potentiometric electrodes, 399 inert metal, 402 metal-metal cation, 400 metal-metal salt, 401 Potentiometric measurement, accuracy, 412 Potentiometric titration, 456 characteristics, 458 pH, 457 precipitation, 457 Potentiometry, 399 Potentiostat, 467 Power analysis, 110 Precipitates, drying, 349 filtering, 348 igniting of, 48, 349 impurities in, 347 organic, 353 washing, 348 Precipitation titrations, 374 potentiometric, 457 Precipitation, potentiometric, 457 minimum solubility, 357 Precision of the mean, 74 Precision, 63, 72 in validation, 138 Preparing the solution, for redox titrations, 454 Primary standard, 167 requirements, 168 Primary standard chemicals, 23 Primer, G6 Principle of electroneutrality, 205 Prism, 506 Probability, 84 Process analysis, 785 instrument requirements, 787 Proficiency testing, 143 Proficiency testing experiment, E84 Propagation of errors, 75 addition and subtraction, 76 multiplication and division, 77 and significant figures, 81 Propagation of uncertainty, 67 Protein identification, G16 Protein-free filtrate, 11, 57 Ba(OH)2 -ZnSO4 , C3 Folin-Wu, C4 trichloroacetic acid, C4 tungstic acid, C4 Proteins, G1 desalting of, 653 Kjeldahl determination, 310 percent nitrogen, 311 Proteome, G13 Proteomics, G13 Pseudo first-order reaction, 771 Pseudo zero-order reaction, enzymatic, 773 Pulsed discharge detector, 634 Pulsed field gel electrophoresis, 710 Purge-and-trap, 642 for indoor/outdoor air monitoring, 642 Purnell equation, 615 Pyrolysis GC, 642 Q Q test, 95 Q values table, 96 QA, see Quality assurance QUA, see Quality assurance unit Quadratic equation, Goal Seek solution of, 198 program for, 199, 258 Quadratic formula, 799 Quadrupole mass analyzer, 756 Qualitative analysis, Quality assurance unit, 134 Quality assurance, 143 Quality control, 143, 785 Quality control chart, 15, 83 Quality control experiment, E82 Quantitative analysis, Quantum yield, 534 R r2 , 105 video, 119 Radiation, absorption of, 480 Radioimmunoassay, C6, C8 Random error, 15, 75 (see also Indeterminate error) Range, efficiency of, 99 in validation, 139 Rate constant, 188, 770 Rate expression, 770 Rate law, 770 Reacting units, acid-base, text website Chp5 reduction-oxidation, text website Chp5 Reaction completion time, first order reaction, 770, 771 second order reaction, 771 Reaction mechanism, 769 Reaction order, 769 Christian7e bindex.tex INDEX 824 Reaction rate, 769 Reaction time, 771 Reagent blank, 64 (see also Blank) Reagent-grade chemicals, 23 Redox indicators, 446 transition range, 446 Redox mediator, 473 Redox reactions, 384 balancing, 437 reacting species, 387 Redox titrants, cerium(IV), 453 iodine, 447 potassium dichromate, 453 potassium permanganate, 452 sodium thiosulfate, 449 Redox titration, potential change required, 442 potentiometric end point detection, 456 preparing the sample, 475 visual end point detection, 445 Redox titration curve, calculation, 441 equivalence point, 441 Reduced velocity, 612 Reducing agent, 384 Reduction potential, 386 Reduction, 383 Reduction-oxidation reactions, see Redox reactions Reference electrode, 400, 404 double junction, 408 SCE, 407 Reference materials, 15 in validation, 138 Reference method, 135 Refractory compound formation, 566 Refractory elements, 560 Regression analysis Excel, 120, 502, 640, 775, 778 Rejection of a result, 95 Relative accuracy, 71 Relative error, 71 Relative method, 13 Relative uncertainty, 67 Reliability, 140 Repeatability, 140 Representative sample, in environmental analysis, EN1 Reproducibility, 140 Residual liquid-junction potential, 411 Response factor, 137 Retention factor, 609, 630 and resolution, 614 Retention time, 607, 621 adjusted, 608 Retention volume, 607 Reversed-phase chromatography, 605, 652 Rf value, 703 RF, see Response factor Riboflavin, fluorescence determination, E57 Robustness, 140 Rohrshneider constant,629 Rotameter, EN4 Rotational transition, 481 Rounding off, 71 V1 - 08/21/2013 12:29 A.M Page 824 Rubber policeman, 47 Ruggedness, 140 S Safety in the laboratory, 57, S1 Safety rules, S1 Salt bridge, 385 Salting out, 217 Sample preparation, solid-phase extraction, 579 solvent extraction, 579 Sample, 49 analysis, 9, 50 dissolution of, 52 drying of, 51 grab, 9, 50 gross, 9, 49 laboratory, minimum size, 112 preparing for analysis, 10 representative, Samples, handling and storing, 10 minimum number of, 108 Sampling, 49 of gases, 50 of liquids, 50 of solids, 50 statistics of, 107 Sandell-Kolthoff reaction, 772 Saturated calomel electrode, 407 Saturated solution, 356 SciFinder Scholar, 794 SCOT columns, 625 SDS-PAGE, 709, G15 Seawater, pH determination, 272 SEC, see Size exclusion chromatography Secondary ion mass spectrometry, 752 Secondary standard, 43, 197, E16 Second-order reaction, 770 Sediment sampling, EN11 Selective, Selectivity coefficient of ISE, fixed interference method, 430 matched potential method, 430 separate solution method, 430 Selectivity, in validation, 136 Semiautomatic instruments, 788 Semimicrobalance, 26 Sensitivity, in validation, 139 Sensor, electrochemical, 472 Separation factor, 615 Separatory funnel, 580 Sephadex, 653 Sequential injection analysis, 791 Serum electrolytes, C4 Serum, SHE, 386 Shotgun genome sequencing, G7, G10 SIA, see Sequential injection analysis Significant figures, 65 addition and subtraction, 67 least-squares line, 120 logarithms, 70 multiplication and division, 67 and propagation of errors, 81 Silver, Volhard determination, E21 Silver nitrate, standard solution, E23 Simultaneous equations, program for, 258 Single-nucleotide polymorphism, G11 (see also SNPs) Single-pan balance, use of, E1 Singlet state, 530 Single-walled carbon nanotubes, 471 Size exclusion chromatography, 605, 653 Slab gel electrophoresis, 708 Slightly soluble substances, 194 Slit width, mechanical, 518 spectral, 518 Slope, spreadsheet calculation, 118 standard deviation of, 102 Snell’s law, 674 SNP analysis, G12 SNPs, G12 Soda ash, determination of, E14 (see also Sodium carbonate) Sodium, flame emission determination, E60 standard solution, E60 Sodium carbonate, primary standard, E15 potentiometric titration, E38 titration, 296 Sodium D-line, 549 Sodium hydroxide , solution preparation, E13 standard solution of, 42 standardization, E13 Sodium ion, activity coefficient in blood, 430 standard activity solutions, 430 Sodium thiosulfate solution, E31 Sodium thiosulfate standardization, 451, E31, E33 Soil sampling, EN11 Solid-phase extraction (see also SPE), 586 dual phases, 590 polymer based, 590 procedure optimization, 589 silica based, 586 sorbents for, 589 of trace organics in water, EN12 universal sorbent, 589 Solid-phase extraction experiment, E61 Solid-phase microextraction, 591 Solid-phase nanoextraction, 593 Solubility product constants, 803 Solubility product, 355 conditional, 367,372 Solubility, acidity effect, 366 calculation of, 356 common ion effect, 356 complexation effect, 372 diverse ion effect, 361 stoichiometry effect, 357 Solvent extraction, accelerated, 585 efficiency, 581 Christian7e bindex.tex INDEX of ion-association complexes, 583 metal chelates, 336 of metal complexes, 584 of metals, 583 microwave-assisted, 585 Solver, buffer calculation, 264 charge balance method titration curve, 285, 293 multiple pH calculations, 258 for spectrophotometric mixture, 500 video, 87 SOPs, see Standard operating procedures Sørenson, Søren, 228 Soxhlet extractor, EN12 SPE (see also solid-phase extraction), 586 SPE, procedure optimization, 589 SPE cartridges, 587 SPE disks, 588 SPE microtiter plates, 589 SPE pipet tips, 587 Specific activity, 774 Specific conductance, 677 Specific gravity, 155 Specific rate constant, 770 Specific resistivity, 679 Specific rotation, 685 Specific, Spectral databases, 493 Spectral slit width, 518 Spectrofluorometer, 535, 536 Spectrometer, visible/UV/IR cells, 509 Spectrometer components, diffraction grating, 506 prism, 506 Spectrometer detectors, IR, 516 UV-vis, 513 Spectrometer sources, 504 infrared, 505 visible, 504 ultraviolet, 505 Spectrometer, 504 absorbance calibration, 518 array, 522 double-beam, 521 IR, 523 near-IR, 548 single-beam, 519 wavelength calibration, 518 Spectrometric error, 526 Spectrometry, 548 of mixtures, 498 quantitative calculations, 494 solvents for, 493 Spectrophotometer, 504 Spectrophotometry, mixture determination, E50 Spectroscopy, 548 Spike, 138 Spike recovery, 138 Spontaneous process, 191 Spreadsheet, calculation of unknown from calibration curve, 502 coefficient of determination calculation, 118 internal standard calibration, 640 V1 - 08/21/2013 12:29 A.M Page 825 825 logarithm concentration diagram, 267 for mixture calculations, 500 for rate calculation, 778 weak acid titration curve, 293 Spreadsheets, 112 absolute cell references, 114 filling cell contents, 112 for graphing, 112 plotting calibration curves, 117 printing, 113 relative cell references, 114 saving, 113 strong acid titration curve, 283 useful syntaxes, 116 web tutorial on use, 112 SRMs, 15 Stability constant, 323 Standard acid, 290 Standard acid solution, preparation of, 42 Standard addition, 14, 461 in atomic spectrometry, 567 in atomic absorption, E59 in gas chromatography, 639 Standard addition calculations, 568 Standard addition experiment, E61 Standard base solution, preparation of, 42 Standard base, 290 Standard buffers, accuracy, 415 temperature dependence, 419 Standard deviation, 72 estimated, 72 of intercept, 102 relative, 74 pooled, 89 of slope, 102 of unknown concentration, 102, 503 video, 116 Standard deviation of regression, 103, 120 Standard electrode potentials, 806 Standard error, 74 Standard error of the estimate, 124 Standard hydrogen electrode, 386 Standard operating procedures, 134 Standard potential, 390 Standard reference materials, 15 in validation, 138 Standard solution, 166, 167 Standard state of solids, 211 Standard state of water, 211 Standardization, 167, 176 calculations, 173 Starch indicator, 446 Starch solution, E30 Stationary phases, see GC, HPLC Stationary phases, in HPLC, 654 Statistical programs, Excel LINEST, 123 Statistics for small data sets, 98 Statistics of sampling, 107 Stern layer, 717 STM, see Sub-two micron phase Stoichiometric calculations, 166 Stoichiometric, 167 Stoichiometry, 149 Stokes-Einstein equation, 677 Stray light, 530 Student t-test, 88 (see also t-test) Sub-two micron phase, 665 Successive approximations, 196 Sulfate, barium titration, 381 gravimetric determination, E9 Sulfur and nitrogen chemiluminescence detectors, 635 Sulfur dioxide determination, EN8 Sulfur GC detector,633 Supersaturation, 344 Supporting electrolyte, 470 Suppressor column, 693 Surface adsorption on precipitates, 347 SWCNTs, 471 Synge, Richard L M , 598 Syntaxes, useful, 116 Syringe pipets, 32 System point, 7.16.2 website Systematic approach to equilibrium calculations, 204 multiple equilibria, 368 steps, 207 Systematic error, 15, 63, 75 (see also Determinate error) Sytematic approach, hints for applying, 208 T Tandem mass spectrometry, 765 TC, 30 TD, 31 Temperature programming, 638 and analyte volatility, 630 Tenax A, 642 Theoretical plate, 607 (see also Plate number) Theory of solvent systems, acid, 224 base, 224 Thermal conductivity detector, 630 Thermal desorption, 641 Thermal noise, 526 Thermal precipitator, EN6 Thermistor, 517 Thermocouple, 516 Thermodynamic equilibrium constant, 217 acid, 226 autoprotolysis, 226 solubility product, 361 Thermopile, 517 Thin-layer chromatography, 702 high performance, 703 mobile phases, 704 sample application, 704 spot detection, 707 stationary phases, 703 quantitative, 707 two-dimensional, 707 Thiocyanate standardization, E22 Thymine, G3 Thymol blue solution, E47 Time domain spectrum, 523 Time-of-flight analyzer, 758 TISAB, 425 TISAB solution preparation, E26 Titer, 179 Christian7e bindex.tex V1 - 08/21/2013 12:29 A.M Page 826 INDEX 826 Titrant, 167 Titrating, tips for, 36 Titration calculations, 173 Titration curve, 282 precipitation, 374 program for, supplement 8.11b website spreadsheet construction for HCl, 283 spreadsheet construction for weak acid, 293 weak acid, 290 weak base, 295 Titration curve of weak base, strong acid, 282 Titration error, 288 Titration methods, kinds of, 168 Titration, 12 requirements, 166 Titrimetric analysis, 12 Titrimetry, origin of, TLC, see Thin-layer chromatography Total hydrocarbon determination, EN8 Total ionic strength buffer, 425 (see also TISAB) Trace organic environmental sampling, EN12 Transcription, G14 Transducer, 472 Transferability, 140 Transmittance, 495 Triplet state, 530 Tris buffers, 264 Tswett, Mikhail, 597 ttest for paired samples, video, 94 t-test, types of situations, 88 t-test, paired, 93 Turnover number, 773 t-values table, 84 Two-dimensional gas chromatography, 645 Two-dimensional GC, 619, 645 (see also GC x GC) Two-dimensional PAGE, G15 U UHPLC, 651, 701 Ultracentifuge, 46 Ultra-high pressure liquid chromatography, 651, 701 Ultramicroelectrode, 474 Uncertainty of unknown, 102, 502 Uncertainty, propagation of, 67 Urea determination, 311, 780 Uric acid determination, 780, C4 V Vacutainer, 43 Vacuum ultraviolet GC detector, 637 Vacuum-UV region, 480 Validation of analytical method, 15, 134 Validation process, 135 minimum number of measurements, 138 Valinomycin, 426 van Deemter, J J., 609 van Deemter equation, 609 reduced form, 612 van Deemter plot, HPLC, 652, 702 Variance, 75, 86, G7 of an analysis, 107 Vectors, G7 Vibrational overtone, 491 Vibrational relaxation, 531 Vibrational transition, 481, 482 Videos, absolute cell reference, 115 average, 116 data analysis regression, 87 equilibrium calculation, 201 error bars, 107 Example 9.6, 339 F-test, 88 Goal Seek equilibrium, 219 Goal Seek pH NH4 F, 238 intercept, 119 introduction to Excel, 113 LINEST, 120 paired t-test from Excel, 94 plotting in Excel, 102, 118 slope, 119 Solver, 87 spreadsheet tutorial basic functions, 112 spreadsheet tutorial graphing, 112 standard deviation, 116 ttest for paired samples, 94 Visible region, 480 Vitamin B2, fluorescence determination, E57 Vitamin C, HPLC determination, E71 Void volume, 608, 614 Volatile organic compound (VOC) sampling, EN6 Volatile organic compounds, GC determination, 643 Volhard determination, E21 Volhard titration, 379 Voltage drop, 467 Voltaic cell, 384 (see also Electrochemical cell) cell convention, 388 with liquid junction, 405 without liquid junction, 404 Voltammetry, 467 potential range, 471 potential required, 468 solid electrode, 471 Voltammogram, 467 Volume/volume basis, 164 Volume/volume gas concentrations, EN2 Volumetric analysis, 12 Volumetric calculations, molarity, 169 normality, text website Chp5 Volumetric flasks, 30 calibration of, 39 Volumetric glassware, calibration of, 37 care of, 35 NIST tolerances, inside back cover precision of, 37 selection of, 41 to contain, 32 to deliver, 31 tolerances of, 37, back cover Volumetric measurements, microplate reader, E4 Von Liebig, Justus, 223 von Wiemarn ratio, 344 W Walsh, Alan, 556 Wash bottle, 45 Water hardness, 166, 334 EDTA determination, E19 microscale titration, E36 Water sample analysis, EN11 Water sampling, EN9 Water, standard state, 211 Wavelength calibration, 518 Wavelength, 479 nominal, 517 Wavenumber, 479 WCOT columns, 624 Web of Knowledge, Web of Science, Weighing boat, 29 Weighing by difference, E2, E15 Weighing dish, 29 Weighing, accurate, 29 by difference, 29 direct, 29 of liquids, 29 of solids, 29 rough, 29 rules for, 28 Weight relationships, 180 Weight, 24 Weight/volume basis, 162 Wet digestion, 11, 52, 53 Wet-test meter, EN4 Wheatstone bridge circuit, 630 Whole genome sequencing, G11 Working electrode, 467 minimum potential for reduction, 468 X Xylene isomers, IR determination, E56 Y Yalow, Roslyn, C7 Z z score, 143 z score experiment, E84 Zero integrated field electrophoresis, 711 Zero point, determination of, E2 Zero point drift, 26 Zeta potential, 717 ZIFE, 711 Zimmermann-Reinhardt reagent, 453 Zwitterion, 309, 691 ... Good Good–moderate Moderate Good Moderate Fast–moderate Moderate Fast Moderate Low–moderate Moderate Moderate–high 2–5 Good Fast–moderate Moderate–high 2–10 Good–moderate Fast–moderate Moderate... curve With modern computer-controlled instruments, this is done electronically or digitally, and direct readout of concentration is obtained METHOD OF STANDARD ADDITIONS Standard additions calibration... spectrometric methods (Chapter 17), and gas and liquid chromatography (Chapters 20 and 21), and added many new Excel problems and exercises Gary compiled and organized all old and new supplementary