Chromatography

download Chromatography

of 957

  • date post

    17-Aug-2014
  • Category

    Documents

  • view

    970
  • download

    5

Embed Size (px)

Transcript of Chromatography

INTRODUCTION TOMODERN LIQUIDCHROMATOGRAPHYThird EditionLLOYD R. SNYDERLC Resources, Inc.Orinda, CAJOSEPH J. KIRKLANDAdvanced Materials TechnologyWilmington, DEJOHN W. DOLANLC Resources, Inc.Amity, ORA John Wiley & Sons, Inc., PublicationINTRODUCTIONTOMODERNLIQUIDCHROMATOGRAPHYThird EditionINTRODUCTION TOMODERN LIQUIDCHROMATOGRAPHYThird EditionLLOYD R. SNYDERLC Resources, Inc.Orinda, CAJOSEPH J. KIRKLANDAdvanced Materials TechnologyWilmington, DEJOHN W. DOLANLC Resources, Inc.Amity, ORA John Wiley & Sons, Inc., PublicationCopyright 2010 by John Wiley & Sons, Inc. All rights reserved.Published by John Wiley & Sons, Inc., Hoboken, New Jersey.Published simultaneously in Canada.Nopartofthispublicationmaybereproduced,storedinaretrievalsystem,ortransmittedinanyformor byanymeans, electronic, mechanical, photocopying, recording, scanning, or otherwise,except aspermittedunderSection107or108of the1976UnitedStatesCopyright Act, withouteither the prior writtenpermission of the Publisher, or authorization throughpayment of theappropriateper-copyfeetotheCopyrightClearanceCenter, Inc., 222RosewoodDrive, Danvers,MA01923,(978)750-8400,fax(978)750-4470,orontheweb atwww.copyright.com.RequeststothePublisherforpermissionshouldbeaddressedtothePermissionDepartment,JohnWiley&Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748-6011, fax (201) 748-6008, or online athttp://www.wiley.com/go/permission.Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best effortsinpreparingthisbook, theymakenorepresentationsorwarrantieswithrespect totheaccuracyor completenessof thecontentsof this bookandspecicallydisclaimanyimpliedwarranties ofmerchantability or tness for a particular purpose. No warranty may be created or extended by salesrepresentativesorwrittensalesmaterials. Theadviceandstrategiescontainedhereinmaynot besuitableforyoursituation.Youshouldconsultwithaprofessionalwhereappropriate.Neitherthepublisher nor author shall be liable for any loss of prot or any other commercial damages, includingbut not limited to special, incidental, consequential, or other damages.For general information on our other products and services or for technical support, please contactour Customer Care Department within the United States at (800) 762-2974, outside the United Statesat (317) 572-3993 or fax (317) 572-4002.Wiley also publishes its books in a variety of electronic formats. Some content that appears in printmay not be available in electronic formats. For more information about Wiley products, visit our website at www.wiley.com.Library of Congress Cataloging-in-Publication Data:Snyder, Lloyd R.Introduction to modern liquid chromatography / Lloyd R. Snyder, Joseph J. Kirkland.3rded. / John W. Dolan.p. cm.Includes index.ISBN 978-0-470-16754-0(cloth)1. Liquid chromatography. I. Kirkland, J. J. (Joseph Jack), 1925- II. Dolan, John W. III.Title.QD79.C454S58 2009543/.84dc222009005626Printed in the United States of America.10 9 8 7 6 5 4 3 2 1CONTENTSPREFACE xxxiGLOSSARY OF SYMBOLS AND ABBREVIATIONS xxxv1 INTRODUCTION 11.1 Background Information, 21.1.1 What Is HPLC?, 21.1.2 What Can HPLC Do?, 41.2 A Short History of HPLC, 61.3 Some Alternatives to HPLC, 81.3.1 Gas Chromatography (GC), 81.3.2 Thin-Layer Chromatography (TLC), 91.3.3 Supercritical Fluid Chromatography(SFC), 101.3.4 Capillary Electrophoresis (CE), 111.3.5 Countercurrent Chromatography, 111.3.6 Special Forms of HPLC, 121.4 Other Sources of HPLC Information, 121.4.1 Books, 121.4.2 Journals, 131.4.3 Reviews, 131.4.4 Short Courses, 131.4.5 The Internet, 13References, 152 BASIC CONCEPTS AND THE CONTROL OF SEPARATION 192.1 Introduction, 202.2 The Chromatographic Process, 202.3 Retention, 24vvi CONTENTS2.3.1 Retention Factor k and Column Dead-Timet0, 252.3.2 Role of Separation Conditions and SampleComposition, 282.3.2.1 Intermolecular Interactions, 302.3.2.2 Temperature, 342.4 Peak Width and the Column Plate Number N, 352.4.1 Dependence of N on SeparationConditions, 372.4.1.1 Band-Broadening Processes ThatDetermine Values of N, 392.4.1.2 Some Guidelines for SelectingColumn Conditions, 462.4.2 Peak Shape, 502.5 Resolution and Method Development, 542.5.1 Optimizing the Retention Factor k, 572.5.2 Optimizing Selectivity , 592.5.2.1 Regular and IrregularSamples, 602.5.3 Optimizing the Column Plate Number N, 612.5.3.1 Effects of Column Conditions onSeparation, 612.5.3.2 Fast HPLC, 632.5.4 Method Development, 652.5.4.1 Assessment of SampleComposition and SeparationGoals, 652.5.4.2 Sample Pretreatment, 662.5.4.3 Selection of ChromatographicMode, 662.5.4.4 Detector Selection, 662.5.4.5 Choice of SeparationConditions, 672.5.4.6 Anticipation, Identification, andSolution of PotentialProblems, 672.5.4.7 Method Validation and SystemSuitability, 692.6 Sample Size Effects, 692.6.1 Volume Overload: Effect of Sample Volumeon Separation, 702.6.2 Mass Overload: Effect of Sample Weight onSeparation, 71CONTENTS vii2.6.3 Avoiding Problems due to Too Large aSample, 732.6.3.1 Higher Than Expected SampleConcentrations, 732.6.3.2 Trace Analysis, 732.7 RELATED TOPICS, 742.7.1 Column Equilibration, 742.7.2 Gradient Elution, 752.7.3 Peak Capacity and Two-dimensionalSeparation, 762.7.4 Peak Tracking, 772.7.5 Secondary Equilibria, 782.7.6 Column Switching, 792.7.7 Retention Predictions Based on SoluteStructure, 802.7.7.1 Solvation-Parameter Model, 82References, 833 EQUIPMENT 873.1 Introduction, 883.2 Reservoirs and Solvent Filtration, 893.2.1 Reservoir Design and Use, 903.2.2 Mobile-Phase Filtration, 913.3 Mobile-Phase Degassing, 923.3.1 Degassing Requirements, 923.3.2 Helium Sparging, 943.3.3 Vacuum and In-line Degassing, 953.4 Tubing and Fittings, 963.4.1 Tubing, 963.4.1.1 Low-Pressure Tubing, 963.4.1.2 High-Pressure Tubing, 973.4.2 Fittings, 993.4.2.1 Low-Pressure Fittings, 993.4.2.2 High-Pressure Fittings, 1013.4.2.3 Specialty Fittings, 1033.5 Pumping Systems, 1043.5.1 Reciprocating-Piston Pumps, 1043.5.1.1 Dual-Piston Pumps, 1083.5.1.2 Accumulator-Piston Pumps, 1083.5.1.3 Active Check Valve, 1093.5.2 On-line Mixing, 1093.5.2.1 High-Pressure Mixing, 1093.5.2.2 Low-Pressure Mixing, 1113.5.2.3 Hybrid Systems, 111viii CONTENTS3.5.3 Gradient Systems, 1123.5.4 Special Applications, 1123.5.4.1 Low-Flow (Micro and Nano)Applications, 1123.5.4.2 High-Flow (Prep)Applications, 1133.5.4.3 High-Pressure Applications, 1133.6 Autosamplers, 1133.6.1 Six-Port Injection Valves, 1143.6.1.1 Filled-Loop Injection, 1143.6.1.2 Partial-Loop Injection, 1153.6.2 Autosampler Designs, 1163.6.2.1 Pull-to-Fill Autosamplers, 1173.6.2.2 Push-to-Fill Autosamplers, 1183.6.2.3 Needle-in-LoopAutosamplers, 1193.6.3 Sample-Size Effects, 1193.6.3.1 Injection Volume, 1203.6.3.2 Injection Solvent, 1213.6.4 Other Valve Applications, 1223.6.4.1 Column Switching, 1223.6.4.2 Fraction Collectors, 1233.6.4.3 Waste Diversion, 1243.7 Column Ovens, 1253.7.1 Temperature-Control Requirements, 1253.7.2 Oven Designs, 1263.7.2.1 Block Heater, 1263.7.2.2 Air Bath, 1263.7.2.3 Peltier Heater, 1263.8 Data Systems, 1273.8.1 Experimental Aids, 1273.8.2 System Control, 1293.8.3 Data Collection, 1293.8.4 Data Processing, 1303.8.5 Report Generation, 1303.8.6 Regulatory Functions, 1303.9 Extra-Column Effects, 1313.10 Maintenance, 1313.10.1 System-Performance Tests, 1313.10.1.1 Installation Qualification,Operational Qualification, andPerformance Qualification, 1323.10.1.2 Gradient Performance Test, 1323.10.1.3 Additional System Checks, 135CONTENTS ix3.10.2 Preventive Maintenance, 1383.10.2.1 Periodic Maintenance, 1383.10.2.2 Suggestions for RoutineApplications, 1413.10.3 Repairs, 1433.10.3.1 Personnel, 1433.10.3.2 Record Keeping, 1433.10.3.3 Specific RepairRecommendations, 144References, 1444 DETECTION 1474.1 Introduction, 1484.2 Detector Characteristics, 1494.2.1 General Layout, 1494.2.2 Detection Techniques, 1514.2.2.1 Bulk Property Detectors, 1514.2.2.2 Sample-Specific Detectors, 1524.2.2.3 Mobile-Phase ModificationDetectors, 1524.2.2.4 Hyphenated Techniques, 1524.2.3 Signal, Noise, Drift, and AssayPrecision, 1524.2.3.1 Noise and Drift, 1534.2.3.2 Signal-to-Noise Ratio (S/N), 1554.2.4 Detection Limits, 1574.2.5 Linearity, 1584.3 Introduction to Individual Detectors, 1604.4 UV-Visible Detectors, 1604.4.1 Fixed-Wavelength Detectors, 1634.4.2 Variable-Wavelength Detectors, 1644.4.3 Diode-Array Detectors, 1654.4.4 General UV-Detector Characteristics, 1664.5 Fluorescence Detectors, 1674.6 Electrochemical (Amperometric) Detectors, 1704.7 Radioactivity Detectors, 1724.8 Conductivity Detectors, 1744.9 Chemiluminescent Nitrogen Detector, 1744.10 Chiral Detectors, 1754.11 Refractive Index Detectors, 1774.12 Light-Scattering Detectors, 1804.12.1 Evaporative Light-Scattering Detector(ELSD), 181x CONTENTS4.12.2 Condensation Nucleation Light-ScatteringDetector (CNLSD), 1824.12.3 Laser Light-Scattering Detectors (LLSD), 1834.13 Corona-Discharge Detector (CAD), 1844.14 Mass Spectral Detectors (MS), 1854.14.1 Interfaces, 1864.14.1.1 Electrospray Interface (ESI), 1864.14.1.2 Atmospheric-PressureChemical-Ionization Interface(APCI), 1874.14.1.3 Other Interface Designs, 1884.14.1.4 Flow-Rate Considerations, 1884.14.2 Quadrupoles and Ion Traps, 1884.14.3 Other MS Detectors, 1904.15 Other Hyphenated Detectors, 1914.15.1 Infrared (FTIR), 1914.15.2 Nuclear Magnetic Resonance (NMR), 1924.16 Sample Derivatization and Reaction Detectors, 194References, 1965 THE COLUMN 1995.1 Introduction, 2005.2 Column Supports, 2005.2.1 Particle Characterization, 2015.2.1.1 Particle Type, 2015.2.1.2 Particle Size and PoreDiameter, 2035.2.2 Silica Supports, 2035.2.2.1 Column Efficiency, 2055.2.2.2 Nature of the Silica Surface, 2085.2.2.3 Particle Preparation, 2115.2.3 Porous Polymers, 2125.2.4 Monoliths, 2125.2.4.1 Silica-Based Monoliths, 2135.2.4.2 Polymer-Based Monoliths, 2145.2.5 Other Inorganic Particles, 2145.2.5.1 Zirconia, 2155.2.5.2 Alumina and Titania, 2175.2.5.3 Graphitized Carbon, 2175.3 Stationary Phases, 2175.3.1 Bonded Stationary Phases, 2185.3.2 Other O