Tài liệu Chemical analysis modern instrumentation methods and techniques 2editon

Chemical Analysis Modern Instrumentation Methods and Techniques Second Edition Francis Rouessac and Annick Rouessac University of Le Mans, France Translated by Francis and Annick Rouessac and Steve Brooks Chemical Analysis Second Edition Chemical Analysis Modern Instrumentation Methods and Techniques Second Edition Francis Rouessac and Annick Rouessac University of Le Mans, France Translated by Francis and Annick Rouessac and Steve Brooks English language translation copyright © 2007 by John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex PO19 8SQ, England Telephone (+44) 1243 779777 Email (for orders and customer service enquiries): [email protected] Visit our Home Page on www.wiley.com Translated into English by Francis and Annick Rouessac and Steve Brooks First Published in French 2nd Edition 3rd Edition 4th Edition 5th Edition 6th Edition © © © © © © 1992 1994 1997 1998 2000 2004 Masson Masson Masson Dunod Dunod Dunod This work has been published with the help of the French Ministère de la Culture-Centre National du Livre All Rights Reserved. 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If professional advice or other expert assistance is required, the services of a competent professional should be sought. Other Wiley Editorial Offices John Wiley & Sons Inc., 111 River Street, Hoboken, NJ 07030, USA Jossey-Bass, 989 Market Street, San Francisco, CA 94103-1741, USA Wiley-VCH Verlag GmbH, Boschstr. 12, D-69469 Weinheim, Germany John Wiley & Sons Australia Ltd, 33 Park Road, Milton, Queensland 4064, Australia John Wiley & Sons (Asia) Pte Ltd, 2 Clementi Loop #02-01, Jin Xing Distripark, Singapore 129809 John Wiley & Sons Canada Ltd, 6045 Freemont Blvd, Mississauga, Ontario, L5R 4JE Canada Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic books. Anniversary Logo Design: Richard J. Pacifico Library of Congress Cataloging in Publication Data Rouessac, Francis. [Analyse chimique. English] Chemical analysis : modern instrumentation and methods and techniques / Francis Rouessac and Annick Rouessac ; translated by Steve Brooks and Francis and Annick Rouessac. — 2nd ed. p. cm. Includes bibliographical references and index. ISBN 978-0-470-85902-5 (cloth : alk. paper) — ISBN 978-0-470-85903-2 (pbk. : alk. paper) 1. Instrumental analysis. I. Rouessac, Annick. II. Title. QD79.I5R6813 2007 543—dc22 2006036196 British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN 978-0-470-85902-5 (HB) ISBN 978-0-470-85903-2 (PB) Typeset in 101/2/121/2pt Times by Integra Software Services Pvt. Ltd, Pondicherry, India Printed and bound in Great Britain by Antony Rowe Ltd, Chippenham, Wiltshire This book is printed on acid-free paper responsibly manufactured from sustainable forestry in which at least two trees are planted for each one used for paper production. Contents Foreword to the first English edition Preface to the first English edition Preface to second edition xiii xv xvii Acknowledgments xix Introduction xxi PART 1 SEPARATION METHODS 1 1 General aspects of chromatography 3 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 General concepts of analytical chromatography The chromatogram Gaussian-shaped elution peaks The plate theory Nernst partition coefficient (K) Column efficiency Retention parameters Separation (or selectivity) factor between two solutes 1.9 Resolution factor between two peaks 1.10 The rate theory of chromatography 1.11 Optimization of a chromatographic analysis 1.12 Classification of chromatographic techniques Problems 2 Gas chromatography 2.1 2.2 2.3 Components of a GC installation Carrier gas and flow regulation Sample introduction and the injection chamber 2.4 Thermostatically controlled oven 2.5 Columns 2.6 Stationary phases 2.7 Principal gas chromatographic detectors 2.8 Detectors providing structural data 2.9 Fast chromatography 2.10 Multi-dimensional chromatography 2.11 Retention indexes and stationary phase constants Problems 3 6 7 9 11 12 14 17 17 19 22 24 27 31 31 33 34 39 39 41 46 50 52 53 54 58 CONTENTS vi 3 High-performance liquid chromatography 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 3.10 3.11 3.12 The beginnings of HPLC General concept of an HPLC system Pumps and gradient elution Injectors Columns Stationary phases Chiral chromatography Mobile phases Paired-ion chromatography Hydrophobic interaction chromatography Principal detectors Evolution and applications of HPLC Problems 4 Ion chromatography 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 Basics of ion chromatography Stationary phases Mobile phases Conductivity detectors Ion suppressors Principle and basic relationship Areas of the peaks and data treatment software External standard method Internal standard method Internal normalization method Problems 5 Thin layer chromatography 5.1 5.2 5.3 5.4 5.5 Principle of TLC Characteristics of TLC Stationary phases Separation and retention parameters Quantitative TLC Problems 6 Supercritical fluid chromatography 6.1 6.2 6.3 6.4 6.5 Supercritical fluids: a reminder Supercritical fluids as mobile phases Instrumentation in SFC Comparison of SFC with HPLC and GC SFC in chromatographic techniques 7 Size exclusion chromatography 7.1 7.2 7.3 7.4 7.5 Principle of SEC Stationary and mobile phases Calibration curves Instrumentation Applications of SEC Problems 63 63 64 65 68 68 70 75 76 78 80 80 87 89 93 93 96 98 100 101 104 105 105 107 110 112 117 117 120 121 122 123 125 127 127 129 130 131 133 135 135 137 138 139 140 143 CONTENTS 8 Capillary electrophoresis and electrochromatography 8.1 8.2 8.3 8.4 8.5 8.6 PART 2 9 From zone electrophoresis to capillary electrophoresis Electrophoretic mobility and electro-osmotic flow Instrumentation Electrophoretic techniques Performance of CE Capillary electrochromatography Problems SPECTROSCOPIC METHODS Ultraviolet and visible absorption spectroscopy 9.1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 9.9 9.10 9.11 9.12 9.13 9.14 9.15 9.16 The UV/Vis spectral region and the origin of the absorptions The UV/Vis spectrum Electronic transitions of organic compounds Chromophore groups Solvent effects: solvatochromism Fieser–Woodward rules Instrumentation in the UV/Visible UV/Vis spectrophotometers Quantitative analysis: laws of molecular absorption Methods in quantitative analysis Analysis of a single analyte and purity control Multicomponent analysis (MCA) Methods of baseline correction Relative error distribution due to instruments Derivative spectrometry Visual colorimetry by transmission or reflection Problems 10 Infrared spectroscopy 10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8 10.9 10.10 The origin of light absorption in the infrared Absorptions in the infrared Rotational–vibrational bands in the mid-IR Simplified model for vibrational interactions Real compounds Characteristic bands for organic compounds Infrared spectrometers and analysers Sources and detectors used in the mid-IR Sample analysis techniques Chemical imaging spectroscopy in the infrared 10.11 Archiving spectra 10.12 Comparison of spectra 10.13 Quantitative analysis Problems vii 145 145 148 152 155 157 159 161 165 167 167 169 171 173 174 176 178 181 186 190 192 193 196 198 200 202 203 207 207 208 208 210 212 212 216 221 225 230 232 233 234 238 CONTENTS viii 11 Fluorimetry and chemiluminescence 11.1 11.2 11.3 11.4 11.5 11.6 11.7 11.8 Fluorescence and phosphorescence The origin of fluorescence Relationship between fluorescence and concentration Rayleigh scattering and Raman bands Instrumentation Applications Time-resolved fluorimetry Chemiluminescence Problems 12 X-ray fluorescence spectrometry 12.1 12.2 12.3 12.4 12.5 12.6 12.7 12.8 12.9 Basic principles The X-ray fluorescence spectrum Excitation modes of elements in X-ray fluorescence Detection of X-rays Different types of instruments Sample preparation X-ray absorption – X-ray densimetry Quantitative analysis by X-ray fluorescence Applications of X-ray fluorescence Problems 13 Atomic absorption and flame emission spectroscopy 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 The effect of temperature upon an element Applications to modern instruments Atomic absorption versus flame emission Measurements by AAS or by FES Basic instrumentation for AAS Flame photometers Correction of interfering absorptions Physical and chemical interferences Sensitivity and detection limits in AAS Problems 14 Atomic emission spectroscopy 14.1 14.2 14.3 14.4 14.5 14.6 14.7 Optical emission spectroscopy (OES) Principle of atomic emission analysis Dissociation of the sample into atoms or ions Dispersive systems and spectral lines Simultaneous and sequential instruments Performances Applications of OES Problems 15 Nuclear magnetic resonance spectroscopy 15.1 General introduction 15.2 Spin/magnetic field interaction for a nucleus 15.3 Nuclei that can be studied by NMR 241 241 243 245 247 249 253 255 256 259 263 263 264 266 271 273 277 278 279 279 281 285 285 288 288 290 291 297 298 302 304 305 309 309 310 311 315 317 321 323 324 327 327 328 331 CONTENTS 15.4 15.5 15.6 15.7 15.8 15.9 15.10 15.11 15.12 15.13 15.14 15.15 15.16 15.17 15.18 15.19 PART 3 Bloch theory for a nucleus of spin number I = 1/2 Larmor frequency Pulsed NMR The processes of nuclear relaxation Chemical shift Measuring the chemical shift Shielding and deshielding of the nuclei Factors influencing chemical shifts Hyperfine structure – spin–spin coupling Heteronuclear coupling Homonuclear coupling Spin decoupling and particular pulse sequences HPLC-NMR coupling Fluorine and phosphorus NMR Quantitative NMR Analysers using pulsed NMR Problems OTHER METHODS 16 Mass spectrometry 16.1 16.2 16.3 16.4 16.5 16.6 16.7 16.8 16.9 16.10 16.11 16.12 16.13 16.14 16.15 16.16 16.17 16.18 Basic principles The magnetic-sector design ‘EB’ or ‘BE’ geometry mass analysers Time of flight analysers (TOF) Quadrupole analysers Quadrupole ion trap analysers Ion cyclotron resonance analysers (ICRMS) Mass spectrometer performances Sample introduction Major vacuum ionization techniques Atmospheric pressure ionization (API) Tandem mass spectrometry (MS/MS) Ion detection Identification by means of a spectral library Analysis of the elementary composition of ions Determination of molecular masses from multicharged ions Determination of isotope ratios for an element Fragmentation of organic ions Problems 17 Labelling methods 17.1 17.2 17.3 17.4 17.5 17.6 The principle of labelling methodologies Direct isotope dilution analysis with a radioactive label Substoichiometric isotope dilution analysis Radio immuno-assays (RIA) Measuring radioisotope activity Antigens and antibodies ix 331 333 335 339 340 341 342 342 344 345 347 352 354 355 356 360 364 367 369 369 372 374 379 381 385 387 389 391 392 397 401 402 404 405 407 408 410 415 419 419 420 421 422 423 425 CONTENTS x 17.7 17.8 17.9 Enzymatic-immunoassay (EIA) Other immunoenzymatic techniques Advantages and limitations of the ELISA test in chemistry 17.10 Immunofluorescence analysis (IFA) 17.11 Stable isotope labelling 17.12 Neutron activation analysis (NAA) Problems 18 Elemental analysis 18.1 18.2 18.3 18.4 18.5 18.6 Particular analyses Elemental organic microanalysis Total nitrogen analysers (TN) Total sulfur analysers Total carbon analysers (TC, TIC and TOC) Mercury analysers Problems 19 Potentiometric methods 19.1 19.2 19.3 19.4 19.5 General principles A particular ISE: the pH electrode Other ion selective electrodes Slope and calculations Applications Problems 20 Voltammetric and coulometric methods 20.1 20.2 20.3 20.4 20.5 20.6 20.7 20.8 20.9 20.10 General principles The dropping-mercury electrode Direct current polarography (DCP) Diffusion current Pulsed polarography Amperometric detection in HPLC and HPCE Amperometric sensors Stripping voltammetry (SV) Potentiostatic coulometry and amperometric coulometry Coulometric titration of water by the Karl Fischer reaction Problems 21 Sample preparation 21.1 21.2 21.3 21.4 21.5 21.6 21.7 21.8 21.9 The need for sample pretreatment Solid phase extraction (SPE) Immunoaffinity extraction Microextraction procedures Gas extraction on a cartridge or a disc Headspace Supercritical phase extraction (SPE) Microwave reactors On-line analysers 426 429 430 431 431 432 437 441 441 442 445 447 447 450 451 453 453 455 457 460 463 463 465 465 467 467 468 470 472 472 478 480 481 484 487 487 488 490 491 493 494 496 498 498 CONTENTS 22 Basic statistical parameters 22.1 22.2 22.3 22.4 22.5 22.6 22.7 22.8 22.9 Mean value, accuracy of a collection of measurements Variance and standard deviation Random or indeterminate errors Confidence interval of the mean Comparison of results – parametric tests Rejection criteria Q-test (or Dixon test) Calibration curve and regression analysis Robust methods or non-parametric tests Optimization through the one-factor-at-a-time (OFAT) experimentation Problems xi 501 501 504 504 506 508 510 511 513 515 516 Solutions 519 Appendix – List of acronyms 561 Bibliography 565 Table of some useful constants 567 Index 569 Foreword to the first English edition In Dutch, scheikunde (German: Scheidekunst = the art of separation) is synonymous with ‘Chemistry’. No chemistry whatsoever without separation, without analysis! And no analysis without ‘Instrumentation Methods and Techniques’, i.e. without the sub-title of the present book! Instrumentation was, for a long time, rather crude by today’s standards: the furnace, the alembic, the separatory funnel, the filter, the balance    Crude, and cheap. Today, no modern analytical laboratory is without M$ investments in optical, mass and NMR spectrometers, in high performance chromatographs, in electro-analytical equipment. But also, how heavy the responsibility resting on the shoulders of the analytical chemist! He is the one who in the first place is responsible for the forced closing of a dioxin-delinquent waste incineration plant, for the approval of a new nonpersistent pesticide, for the demotion of an athlete from his Olympic title for having used illegal drugs, for the identification of a criminal by the traces of gunpowder on his hands, for the quantification of environmental contaminants, for the detection of diabetes or of poisoning, for the establishment and the enforcement of standards used in World trade    The analyst, with his power to say ‘yes’ or ‘no’, is one of the most influential of our contemporaries! There are many books on analytical chemistry, but there were very few, and rather old ones, in French, until F. and A. Rouessac published the first French edition of the present book, eight years ago: they had a niche to fill. Four successive editions have confirmed that they had filled it well: their book was simple, highly informative, and it was kept up-to-date. Through its successive improvements, it has become mature for translation. I am sure the present English version, for which I see no equivalent, will now be useful world-wide to students, as well as to professionals. Fare well, Rouessac & Rouessac! 14 February 2000 Guy Ourisson President of the French Academy of Sciences Preface to the first English edition The book entitled Analyse Chimique. Methodes et techniques instrumentals modernes, written originally in French by Professor F. Rouessac and his wife A. Rouessac, has been revised several times and is now in its 4th edition. It is an ongoing project that provides updated versions and increases the usefulness of the manuscript. The purpose of the work has been to provide basic information on methods of chemical analysis and new instrumentation techniques that have been developed and improved in recent years. Its objective is to provide the analyst with a reference manual while providing students with a teaching tool that covers the basics of most instrumental techniques presently used in chemical analysis. It incorporates basic principles, describes commonly used instruments and discusses the main application for most of the analytical techniques. The book classifies methods of analysis according to three categories: separation techniques, spectroscopy techniques and other methods. It was written for undergraduate students in chemistry but with the view that it may be of interest for students in other disciplines (physics, biology, etc.) where chemical methods of analysis and instrumental techniques are used. Thus, it provides sufficient information to understand the techniques and their application and allows students to find additional information in more advanced works that discuss specialised instrumental techniques in more detail. Professor Rouessac gathered the material presented in this book during his teaching career at the University of Le Mans and he has made an effort to integrate theory and practice in a remarkable way. The chapters contain detailed descriptions of instruments and techniques with a few applied examples that are useful to appreciate the scope of the techniques as well as their strengths and limitations in the applied world. The philosophy behind the manuscript is to show that although analytical chemistry and chemical analysis are sometimes considered as different topics, they are inherently intertwined. Over the years, we have seen a tremendous evolution in chemical analysis. Because of developments in electronics and computer sciences, many new approaches have been developed based on physical measurements and these approaches are now widely used. Nowadays, there is a legion of instrumentation techniques that are more sensitive, more selective and can be applied to analytical problems in many areas of science where the structure determination and quantisation of chemical species is needed. For example, physical methods of chemical xvi PREFACE TO THE FIRST ENGLISH EDITION analysis are being used overwhelmingly in the biological sciences. Moreover, the combination of two or more instrumentation analysis techniques had led to the introduction of hyphenated methods that are extremely powerful and require the basic knowledge of the underlying principles. This manuscript provides the essential knowledge for the understanding of these techniques and opens the door to their areas of applications. It also treats some older techniques that maintain their important place in industrial processes. It has been a pleasure for us to translate Professor Rouessac’s work. Although we have been able to translate the technical material relatively precisely, there is a flavour of expression used by the authors in their native language that cannot be transposed, as is usually the case with translations. In spite of this limitation, we believe that the content of this book will be extremely useful to readers that are seeking knowledge and information on chemical analysis and analytical instrumentation. Michel J. Bertrand, Professor Karen C. Waldron, Assistant Professor Department of Chemistry Université de Montréal September 1999 Preface to second edition This textbook presents an explanatory and exploratory review of the basic concepts behind the methodologies most frequently encountered in the qualitative, quantitative and structural chemical analysis employed in sectors as diverse as the chemical, pharmaceutical, food and agricultural industries as well as those areas of the environment subjected to stringent controls. The techniques under review have been classed into one of the following three categories: Separative Methods, Spectral Methods and Other Methods, each of which is the object of an investigative study of the fundamental ideas, their extension, development and application to the corresponding principal, instrumental techniques. Each chapter is illustrated by photographs, numerous diagrams and schemes of chemical reactions or technical principles many of which have been inspired by real instruments and documents obtained from the constructors. However, in order that the book be contained within a reasonable volume, those methods rarely used, or currently in regression are not discussed. Written and presented as comprehensively as possible, the text addresses a broad spectrum of techniques relevant to a wide range of subjects in chemistry, physics and applied biology and will prove appropriate for students of pre-university, undergraduate and postgraduate levels. Specialist technicians in university support, research and industrial training services will equally find this book useful. The current needs of certain professional sectors in chemical analysis, some of which may appear to have been neglected, linked with the increasing choice of techniques and instruments available, equally justify this compendium of information which updates and unifies several previously available texts. Though aimed at an otherwise broad readership, this book has been principally designed to engage the interest of students of chemical analysis and to harness their appreciation of the subject as a particular tool employed in a great many experimental sciences and a variety of associated domains. The authors have included reminders of fundamental principles and have taken account of the evolution of knowledge and the developments in approaches to physical and mathematical phenomena. The text contains only a minimum of theory in order not to lose the attention of the broader readership whose interest is preferential for the technical content. Those readers so wishing may undertake the reading of the more specialised œuvres without major difficulty, having acquired from this book a suitable introduction to both the current methods and practical aspects. The content also reflects the profound changes in analytical techniques currently employed in laboratories. The inherent changes resulting from the growth in demand, the now quite necessary volume of data to be treated, from computerisation and the new requirements most notably in trace analysis. xviii PREFACE TO SECOND EDITION Comprising a discussion of more than twenty methods, which bearing in mind the large number of applications for each capable of being the subject of a lengthy review, along with the addition of individual exercises, (problems and solutions) and the whole delivered in less than 580 pages, the authors have responded to a considerable challenge. They have preferred a format limited to the presentation of the tools themselves rather than to descriptions of all that their use permits them to do. The choice of applications has therefore been simplified to those which express an illustrative value. The origin of this book has been the coursework, accumulated over a number of years, which has been presented to the students of the Institute of Technology at the University of Le Mans, France. Colleagues and friends have given graciously of their time for both the re-reading of the text and for critical suggestions. This version of Chemical Analysis is the 2nd International Edition and has been updated and completed with respect to its predecessor. The fifth edition of this book has equally been translated into Spanish. The title is Anàlisis Quimico. Methodos y Técnicas Instrumentales Modernas, McGraw-Hill Interamerica de Espana, S.A.U. F. & A. Rouessac Le Mans, December 2005 Acknowledgments We are very pleased that the 2nd English edition of Analyse Chimique has been published. The authors wish to thank professors Karen Waldron and Michel Bertrand of the University of Montreal for the very hard work they did in translating the manuscript that was used for the first English edition (John Wiley, 2000). The present text leans on this translation, a large part of it being kept. We also acknowledge Dr Steve Brooks of the Institut de Génétique et de Biologie Moléculaire et Cellulaire in Strasbourg, who translated the text of the French 5th edition. Finally, we have reworked all the chapters and included improved drawings into the text. The authors also wish to express their gratitude to Professor Guy Ourisson, former President of the French Académie des Sciences, who in agreeing to write a forward for previous editions of this book, bestowed upon it a great honour. Sadly Professor Ourission passed away in November 2006. Our special thanks also to the staff of John Wiley & Sons, Ltd (Chichester). We are especially indebted to the following for their kind assistance: Andy Slade, Robert Hambrook, Elizabeth Kingston, Alison Woodhouse (freelance copy-editor) and also Sunita Jayachandran of Integra Ltd (India) for producing a book of pleasing appearance. Those we have inadvertently missed have our sincere apologies. Below is a list of the companies that have graciously agreed to provide us with both information and documents, certain of which have been reproduced within the text. Their assistance has been particularly precious in view of the speed of technological progress in the sector of analytical instrumentation. Agilent Technologies, Alltech Associates Inc, American gas & Chemical Co., American Stress Technologies, Amptek Inc, Analytical Instruments, Anotec, Antek, Arelco, ARL, Asoma, ATI Unicam, ATMI Sensoric Div., ATS, Aurora, Beckman Coulter Inc, Berger Mettler Toledo, Bio-Rad, Bosch, Bruker, BW Technologies, Camag, Carbone-Lorraine, Chrompack, Ciba, CTTM, Daiiso Company, Desaga, Dionex, DuPont, Edinburgh sensors, EG&G-ORTEC, ETP Scientific, Eurolabo, Finnigan, Fisons-Instruments, Foxboro, Galileo, Genesis Lab Syst. Inc., Gilson, Grasby-Electronics, Hamamatsu, Hamilton, Imaging Sensing Technology, Jeol, Jenway, Jobin-Yvon, Jordan Valley, Labsystems, LaMotte Co., Leeman