Handbook of Spectroscopy Edited by G. Gauglitz and T. Vo-Dinh WILE WILEY-VCH Gmbh Co KGaA lSBN3-527-29782-0
Handbook of Spectroscopy Edited by G. Gauglitz and T. Vo-Dinh Handbook of Spectroscopy. Edited by Günter Gauglitz and Tuan Vo-Dinh Copyright 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN 3-527-29782-0
Prof Dr. Guenter Gauglitz This book was carefully produced. Never te for Physical and Theoretical theless, editors, authors and publisher do Chemistry not warrant the information contained of Tubingen therein Readers are Auf der Morgenstelle 8 advised to keep in mind that statements, other items may inadvertently be inaccurate. Prof. Dr. Tuan Vo-Dinh Library of Congress Card No. applied for Advanced Biomedical Science A catalogue record for this book is availabl and Technology Group from the British Library. Oak Ridge National Laboratory P O. Box 2008 Bibliographic information published by Oak Ridge, Tennessee 37831-6101 Die Deutsche Bibliothek USA Die Deutsche Bibliothek lists this publication detailed bibliographic data is available in the E 2003 WILEY-VCH Verlag GmbH& Co KGaA Weinheim All rights reserved (including those of translation in other languages). No part of this book may be reproduced in any form sion from the publishers. Registered na trademarks. etc used in this book when not specifically marked as such, not to be considered unprotected by law Printed in the Federal Republic of Germany Printed on acid-free paper. Typesetting Hagedorn Kommunikation rinting Strauss Offsetdruck GmbH sBN3-527-29782-0
Prof. Dr. Guenter Gauglitz Institute for Physical and Theoretical Chemistry University of Tübingen Auf der Morgenstelle 8 72976 Tübingen Germany Prof. Dr. Tuan Vo-Dinh Advanced Biomedical Science and Technology Group Oak Ridge National Laboratory P. O. Box 2008 Oak Ridge, Tennessee 37831-6101 USA This book was carefully produced. Nevertheless, editors, authors and publisher do not warrant the information contained therein to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. Library of Congress Card No.: applied for A catalogue record for this book is available from the British Library. Bibliographic information published by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data is available in the Internet at http://dnb.ddb.de. 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim All rights reserved (including those of translation in other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Printed in the Federal Republic of Germany. Printed on acid-free paper. Typesetting Hagedorn Kommunikation, Viernheim Printing Strauss Offsetdruck GmbH, Mörlenbach Bookbinding J. Schäffer GmbH & Co. KG, Grünstadt ISBN 3-527-29782-0
Contents Volume 1 Preface XXVIII List of contributors Section I Sample Preparation and Sample Pretreatment 1 Introduction 3 Collection and Preparation of Gaseous Samples 4 Introduction 4 Sampling considerations 5 Active vs Passive Sampling 8 1.3.1 Active air Collection methods 8 1.3.1.1 Sorbents 9 1.3.1.2 Bags 11 1.3.1.3 Canisters 11 1.3.14 Bubblers 12 1.3.1.5 Mist Chambers 13 1.3.2 Passive Sampling 13 Extraction and Preparation of Samples 14 Summary 15 mple Collection and Preparation of Liquid and Solids 17 Introduction 17 Collection of a Representative Sample 1 2.2.1 Statistics of Sampling 18 2.2.2 How Many Samples Should be Obtained? 21 2.2.3 Sampling 2.2.3.1 Liquids 22 2.2.3.2 Preparation of Samples for Analysis 24 时沿 H Verlag gmbh &Co KGaA, Weinheim and luan Vo. Dinh lSBN3-527-29782-0
Contents Volume 1 Preface XXVIII List of Contributors Section I Sample Preparation and Sample Pretreatment 1 Introduction 3 1 Collection and Preparation of Gaseous Samples 4 1.1 Introduction 4 1.2 Sampling considerations 5 1.3 Active vs. Passive Sampling 8 1.3.1 Active Air Collection Methods 8 1.3.1.1 Sorbents 9 1.3.1.2 Bags 11 1.3.1.3 Canisters 11 1.3.1.4 Bubblers 12 1.3.1.5 Mist Chambers 13 1.3.1.6 Cryogenic Trapping 13 1.3.2 Passive Sampling 13 1.4 Extraction and Preparation of Samples 14 1.5 Summary 15 2 Sample Collection and Preparation of Liquid and Solids 17 2.1 Introduction 17 2.2 Collection of a Representative Sample 17 2.2.1 Statistics of Sampling 18 2.2.2 How Many Samples Should be Obtained? 21 2.2.3 Sampling 22 2.2.3.1 Liquids 22 2.2.3.2 Solids 23 2.3 Preparation of Samples for Analysis 24 Contents V Handbook of Spectroscopy. Edited by Günter Gauglitz and Tuan Vo-Dinh Copyright 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN 3-527-29782-0
2.3.1 2.3.1.1 Sample Preparation for Inorganic Analysis 25 3.1.2 Decomposition of Organics 28 2.3.2 iquid Samples 29 2.3.2.1 Extraction/Separation and Preconcentration 29 2.3.2.2Chro Section II Methods 1: Optical Spectroscopy 37 3 Basics of Optical Spectroscopy 39 3.2 Infrared Spectroscopy 41 Raman Spectroscopy 43 3.4 UV/VIS Absorption and Luminescence 44 Instrumentation 48 MIR Spectrometers 4. Dispersive Spectrometers 49 4.1.2 Fourier-Transform Spectrometers 50 4.1.2.1 Detectors 53 4.1.2.2 Step-scan Operation 53 4.1.2.3 Combined technic ques 54 NIR Spectrometers 54 4.2.1 FT-NIR Spectrometers 55 4. 2.2 Scanning- Grating Spectrometers 55 4.2.3 Diode Array Spectrometers 56 4.2.4 4.2.5 LED Spectrometers 56 4.2.6 Raman Spectrometers 57 4.3.1 Raman Grating Spectrometer with Single Channel Detector 57 4.3.1.1 Detectors 59 4.3.1.2 Calibration 60 4.3.2 FT-Raman Spectrometers with Near-Infrared Excitation 61 4.3.3 Raman Grating Polychromator with Multichannel Detector 61 4.4 UV/VIS Spectrometers 63 4.4.1 Sources 64 4.4.2 Monochromators Detectors 64 Fluorescence Spectrometers 66 Measurement Techniques 70 Transmission Measurements 71 Reflection Measurements 73 5.2.1 External Reflection 73
2.3.1 Solid Samples 24 2.3.1.1 Sample Preparation for Inorganic Analysis 25 2.3.1.2 Decomposition of Organics 28 2.3.2 Liquid Samples 29 2.3.2.1 Extraction/Separation and Preconcentration 29 2.3.2.2 Chromatographic Separation 31 Section II Methods 1: Optical Spectroscopy 37 3 Basics of Optical Spectroscopy 39 3.1 Absorption of Light 39 3.2 Infrared Spectroscopy 41 3.3 Raman Spectroscopy 43 3.4 UV/VIS Absorption and Luminescence 44 4 Instrumentation 48 4.1 MIR Spectrometers 48 4.1.1 Dispersive Spectrometers 49 4.1.2 Fourier-Transform Spectrometers 50 4.1.2.1 Detectors 53 4.1.2.2 Step-scan Operation 53 4.1.2.3 Combined Techniques 54 4.2 NIR Spectrometers 54 4.2.1 FT-NIR Spectrometers 55 4.2.2 Scanning-Grating Spectrometers 55 4.2.3 Diode Array Spectrometers 56 4.2.4 Filter Spectrometers 56 4.2.5 LED Spectrometers 56 4.2.6 AOTF Spectrometers 56 4.3 Raman Spectrometers 57 4.3.1 Raman Grating Spectrometer with Single Channel Detector 57 4.3.1.1 Detectors 59 4.3.1.2 Calibration 60 4.3.2 FT-Raman Spectrometers with Near-Infrared Excitation 61 4.3.3 Raman Grating Polychromator with Multichannel Detector 61 4.4 UV/VIS Spectrometers 63 4.4.1 Sources 64 4.4.2 Monochromators 64 4.4.3 Detectors 64 4.5 Fluorescence Spectrometers 66 5 Measurement Techniques 70 5.1 Transmission Measurements 71 5.2 Reflection Measurements 73 5.2.1 External Reflection 73 VI Contents
Contents VII Reflection Absorption 75 5.2.3 Attenuated Total Reflection(ATR)75 5.2.4 Reflection at Thin Films 77 5.2.5 Diffuse Reflection 78 Spectroscopy with Polarized Light 81 5.3.2 Circular Dichroism(CD)82 Photoacoustic measu Microscopic Measurements 84 5.5.1 Infrared Microscopes85 onfocal Microscopes 85 5.5.3 Near-field Microscopes 6 Applications 89 Mid-Infrared(MIR)Spectroscopy 89 6.1.1 Sample Preparation and Measurement 89 6.1.1.1 Gases90 6.1.1.2 Solutions and Neat Liquids 91 6.1.1.3 Pellets and mulls 92 6.1.1.4 Neat Solid Samples 94 6.1. 1.5 Reflection-Absorption Sampling Technique 94 6.1.1.6 Sampling with the ATR Technique 95 6.1. 1.7 Thin Samples 96 6.1. 1.8 Diffuse Reflection Sampling Technique 97 6.1.1.9 Sampling by Photoacoustic Detection 97 6.1.1.10 Microsampling 98 6.1.2 Structural Analysis 98 6.1.2.1 The Region from 4000 to 1400 cm-1 102 6.1.2.2 The Region 1400-900 cm 102 6.1.2.3 The Region from 900 to 400 cm-102 6.1.3 Special Applications 103 Near-Infrared Spectroscopy 104 6.2.2 Applications of NIR Spectroscopy 110 o5 6.2.1 Sample Preparation and Measurement Raman Spectroscopy 112 6.3.1 Sample Preparation and Measurements 112 6.3.1.1 Sample Illumination and Light Collection 113 6.3.1.2 Polarization measurements 118 6.3.1.3 Enhanced Raman Scattering 119 6.3.2 Special Applications 120 UV/VIS Spectroscopy 125 6.4.1 Sample Preparation 125 Structural Analysis 129 6.4.3 Special Applications 132 cence Spectroscopy 135
5.2.2 Reflection Absorption 75 5.2.3 Attenuated Total Reflection (ATR) 75 5.2.4 Reflection at Thin Films 77 5.2.5 Diffuse Reflection 78 5.3 Spectroscopy with Polarized Light 81 5.3.1 Optical Rotatory Dispersion 81 5.3.2 Circular Dichroism (CD) 82 5.4 Photoacoustic Measurements 83 5.5 Microscopic Measurements 84 5.5.1 Infrared Microscopes 85 5.5.2 Confocal Microscopes 85 5.5.3 Near-field Microscopes 86 6 Applications 89 6.1 Mid-Infrared (MIR) Spectroscopy 89 6.1.1 Sample Preparation and Measurement 89 6.1.1.1 Gases 90 6.1.1.2 Solutions and Neat Liquids 91 6.1.1.3 Pellets and Mulls 92 6.1.1.4 Neat Solid Samples 94 6.1.1.5 ReflectionAbsorption Sampling Technique 94 6.1.1.6 Sampling with the ATR Technique 95 6.1.1.7 Thin Samples 96 6.1.1.8 Diffuse Reflection Sampling Technique 97 6.1.1.9 Sampling by Photoacoustic Detection 97 6.1.1.10 Microsampling 98 6.1.2 Structural Analysis 98 6.1.2.1 The Region from 4000 to 1400 cm1 102 6.1.2.2 The Region 1400900 cm1 102 6.1.2.3 The Region from 900 to 400 cm1 102 6.1.3 Special Applications 103 6.2 Near-Infrared Spectroscopy 104 6.2.1 Sample Preparation and Measurement 105 6.2.2 Applications of NIR Spectroscopy 110 6.3 Raman Spectroscopy 112 6.3.1 Sample Preparation and Measurements 112 6.3.1.1 Sample Illumination and Light Collection 113 6.3.1.2 Polarization Measurements 118 6.3.1.3 Enhanced Raman Scattering 119 6.3.2 Special Applications 120 6.4 UV/VIS Spectroscopy 125 6.4.1 Sample Preparation 125 6.4.2 Structural Analysis 129 6.4.3 Special Applications 132 6.5 Fluorescence Spectroscopy 135 Contents VII