JOURNAL OF CHROMATOGRAPHY LIBRARY - VOLUME 24 chemical methods in gas chromatography This Page Intentionally Left Blank JOURNAL OF CHROMATOGRAPHY LIBRARY - volume 24 chemical methods in gas chromatography UG.Berezkin Institute of Petrochemical Synthesis, Academy of Sciences of the U.S.S R., Moscow, U.S.S.R ELSEVIER AMSTERDAM OXFORD - NEW YORK- TOKYO 1983 ELSEVIER SCIENCE PUBLISHERS B.V Molenwerf P.O Box 21 1, 1000 A E Amsterdam, The Netherlands Distributors for the United Srates and Canada: ELSEVIER SCIENCE PUBLISHING COMPANY INC 52, Vanderbilt Avenue New York,NY 10017 Library of Congress Cataloging in Publication Data Eerezkin, V G (Viktor Grigor'evich), 1931Chemical methods in gas chromatography ( J c u r n a l of chromatography library ; v 24) Includes hiblicgraphical references and index Gas chroiuatograpu I Title 11 Series QD79.Ch5B45 1983 543l.0696 ISBN 0-LU-41951-9 (U.S.) ,53-1667 ISBN 0-444-41951-9 (Val 24) ISBN 044441616-1 (Series) Elsevier Science Publishers B.V., 1983 All rights reserved NO part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or b y any means, electronic, mechanical, photocopying, recording or otherwise, without the prior written permission of the publisher, Elsevier Science Publishers B.V., P.O Box 330,1000 AH Amsterdam, The Netherlands Printed in The Netherlands Contents , ., Introduction References Journal of Chromatography Library Chapter Application of chemical methods to the pre-treatment of samples before chromato graphic separation 1.1, Introduction 1.2 Peculiarities of the elaboration of techniques 1.3 The main methods used to obtain derivatives for gas chromatography 1.3.1 Silyl derivatives 1.3.2 Esters 1.3.2.1 The diazomethane method 1.3.2.2 The methanol method , 1.3.2.3 The pyrolysis method 1.3.3 Ethers 1.3.4 Acyl derivatives 1.3.5 Oximes and hydrazones 1.3.6 Derivatives of inorganic compounds 1.4 Application of the chemical formation of derivatives method 1.4.1 Alcohols and phenols 1.4.2 Aldehydes and ketones , 1.4.3 Amines 1.4.4 Carboxylic acids 1.4.5 Analysis of inorganic acids and metals 1.5 Conclusion References Chapter Kinetic methods in gas chromatography References VII 14 15 15 30 45 47 41 41 47 48 49 49 50 50 51 51 51 53 53 54 55 56 67 82 Chapter Pyrolysis-gas chromatography 85 3.1 Introduction , 85 3.2 Equipment and experimental procedure a9 3.3 Identification of substances 112 3.4 Determination of the composition of polymer systems and the structure of polymers 121 3.5 Conclusion 131 References 132 Chapter Determination of the carbon skeleton in organic compounds References Chapter Subtraction method 5.1 Principle of the method 5.2 Application to the identification of the components of test mixtures 5.3 Application t o impurity analysis 5.4 Prospects for development of the method , References Chapter Chemically selective stationary phases References 139 154 157 157 164 178 180 181 185 204 v1 CONTENTS Chapter Reaction gas chromatographic methods of elemental analysis 7.1 Introduction 7.2 Determination of carbon and hydrogen 7.3 Determination of nitrogen 7.4 Determination of sulphur 7.5 Determination of oxygen 7.6 Determination of other elements 7.7 Eleniental analysis of gas chromatographically separated fractions 7.8 Conclusion References 209 209 213 218 225 229 232 233 243 243 Chapter Reaction methods of trace analysis 8.1 Introduction 8.2 Increasing the retention time of the main and trace components or their derivatives 8.3 Decreasing the retention time o f the main and trace components or their derivatives 8.4 Improvement of detection characteristics 8.5 Conclusion References 249 249 250 261 267 279 280 ~ Chapter Functional group analysis 9.1 Introduction 9.2 Specific features of chemico-chromatographic methods of functional group analysis 9.3 Preliminary reactions 9.4 Readions after gas chromatographic separation 9.5 Methods of analysis of main functional groups 9.5.1 Determination of active hydrogen 9.5.2 Determination of amino groups 9.5.3 Determination of main oxygen-containing groups 9.5.4 Determination of some sulphur-containing groups 9.5.5 Determination of alkoxy groups 9.5.6 Determination of sulphur-, nitrogen- and silicon-alkyi groups 9.5.7 Determination of vinyl and alkyl groups 9.5.8 Determination of compounds with unsaturated bonds 9.6 Conclusion References Subject lndex 287 287 288 288 292 296 296 297 298 299 300 301 302 302 304 305 311 JOURNAL OF CHROMATOGRAPHY LIBRARY A Series of Books Devoted to Chromatographic and Electrophoretic Techniques and their Applications Although complementary to the Journal of Chromatography, each volume in the library series is an important and independent contribution in the field of chromatography and electrophoresis The library contains no material reprinted from the journal itself Volume Chromatography of Antibiotics by G.H Wagman and M.J Weinstein Volume Extraction Chromatography edited by T Braun and G Ghersini Volume Liquid Column Chromatography A Survey of Modern Techniques and Applications edited by Z Deyl, K Macek and J Janik Volume Detectors in Gas Chromatography by J SevEik Volume Instrumental Liquid Chromatography A Practical Manual on HighPerformance Liquid Chromatographic Methods by N.A Parris Volume Isotachophoresis Theory, Instrumentation and Applications by F.M Everaerts, J.L Beckers and Th.P.E.M Verheggen Volume Chemical Derivatization in Liquid Chromatography by J.F Lawrence and R.W Frei Volume Chromatography of Steroids by E Heftmann Volume HPTLC - High Performance Thin-Layer Chromatography edited by A Zlatkis and R.E Kaiser Volume 10 Gas Chromatography of Polymers by V.G Berezkin, V.R Alishoyev and 1.B; Nemirovskaya Volume 11 Liquid Chromatography Detectors by R.P.W Scott Volume 12 Affinity Chromatography by J TurkovP Volume 13 Instrumentation for High-PerformanceLiquid Chromatography edited by J.F.K Huber Volume 14 Radiochromatography The Chromatography and Electrophoresis of Radiolabelled Compounds by T.R Roberts VIII JOURNAL OF CHROMATOGRAPHY LIBRARY Volume 15 Antibiotics Isolation, Separation and Purification edited by M.J.Weinstein and G.H Wagman Volume 16 Porous Silica Its Properties and Use as Support in Column Liquid Chromatography by K.K Unger Volume 17 75 Years of Chromatography - A Historical Dialogue edited by L.S Ettre and A Zlatkis Volume 18A Electrophoresis A Survey of Techniques and Applications Part A: Techniques edited by Z Deyl Volume 18B Electrophoresis A Survey of Techniques and Applications Part B: Applications edited by Z Deyl Volume 19 Chemical Derivatization in Gas Chromatography by J Drozd Volume 20 Electron Capture Theory and Practice in Chromatography edited by A Zlatkis and C.F Poole Volume Environmental Problem Solving using Gas and Liquid Chromatography by R.L Grob and M.A Kaiser Volume 22A Chromatography Fundamentals and Applications of Chromatographic and Electrophoretic Methods Part A: Fundamentals edited by E Heftmann Volume 22B Chromatography Fundamentals and Applications of Chromatographic and Electrophoretic Methods Part B: Applications edited by E Heftmann Volume 23A Chromatography of Alkaloids Part A: Thin-Layer Chromatography by A Baerheim Svendsen and R Verpoorte Volume 24 Chemical Methods in Gas Chromatography by V.G Berezkin The author dedicates this book to the memoly of his parents 304 I.’UNCTIONAL GROUP ANALYSIS The main products {depending on the structure and number of unsaturated bonds in the molecule) are formaldehyde, acetaldehyde, acetone (in the presence of an isopropylidene group), glyoxal (especially in the case of compounds with conjugated double bonds), carbon dioxide (in the presence of cumulated bonds) and other aldehydes and aldoesters Ozonides are decomposed thermally 1242, 2431 or by triphenylphosphine powder [238-241, 2441 For thermal decomposition a micro-reactor is applied [245] in which a sample of volume up t o p l can be ozonized, decomposed and injected into a gas chromatograph without losses of the compound The determination of bifunctional compounds was reviewed by Poole and Zlatkis (2671 Only a few reagents capable of forming cyclic derivatives with bifunctional compounds have been described in the literature Boronic acids are applicable to a wide range of bifunctional compounds All of these reactions are highly selective, and some reagents have been developed that also have a high detection selectivity These are of particular interest for the analysis of a few bifunctional components in a complex matrix without the need for a tedious sample clean-up [267] The analysis of organic compounds by ozone reaction GC was described in ref 268 The double-bond analyser was based on the chemical reaction between ozone and alkene after separation, the decrease in ozone concentration being measured by UV absorption The technique simplified the identification of peaks, increased the effectiveness of the analysis and eliminated the overlapping of peaks 9.6 CONCLUSION To conclude our discussion of chemico-chromatographic methods of determining functional groups, it seems interesting to note that chemical ionization in mass spectrometry can be considered as a type of selective functional group analysis Depending on the reagent used in chemical ionization one can record different mass spectra corresponding to the reaction products formed by the reagent with an ion used for its ionization 1246, 2471 Thus, for instance, deuterium oxide is an excellent reagent in the method of chemical ionization for determining active hydrogen in organic compounds and differentiating primary, secondary and tertiary amines 12481 Ammonia is a selective reagent for determining the molecular weight of polyfunctional organic compounds and for the selective ionization of the main type of components in complex organic mixtures [249] Nitrogen oxide is used in the method of chemical ionization for functional group analysis [ S O ] It should also be noted that the methods developed for 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232 233 234 235 236 237 238 39 240 241 242 243 244 245 Subject Index The main objective of this book is to consider methods for analytical reaction gas chromatography Therefore, the Subject Index essentially refers to general methods for solving practical problems; hence, the index is mainly methodical The author feels that an index of this type is in the interest of the readers in that the book may be used more effectively for routine work Analytical gas chromatography, as hybrid method -, limitations 15 Analytical methods, classification -, distribution of publications 1, -,hybrid 1, Analytical reaction gas chromatography, application 4, 15 -, comparison with “classical” chromatography _ ,definition , ,task Carbon skeleton determination 139-156 -,advantages 140 -, as identification method 139 -, in different types of compounds 147 -, methods, dehydrogenation 141, 142 -,-,hydrogenation 140,141 -, -, hydrogenolysis 141,146 -_ , , methylation 139 -, using capillary chromatography 51 Chemical formation of derivatives, as potential source of errors -, converting non-volatile into volatile compounds 15-23 -_ ,converting unstable into stable compounds 15-23 -,criteria of choosing possible reactions 31 -,derivatives of inorganic compounds 50,51 -,disadvantages 30 -,esters 47-49 -, ethers 49,50 -,hydrazones 50 -, improvement of quantitative characteristics of determinations 217 -, improvement of separation 23 -,increase in the sensitivity of detection 29 -, ligand-vapour method 32 -, methylenation by diazomethane 38-40 -, obtaining compounds for calibration 29, 30 ,oximes 50 , reagent-vapour method 32 -, silyl derivatives 47 -,using compounds labelled with stable isotopes 28,29 Chemically selective stationary phases 185 208 -,copper stearates 197 -, crystallohydrates 199 -, dicarbonylrhodium (3-trifluoroacetyl camphorate) 193,194 -, Ndodecylsalicylaldimines 196 ,formed complex metal ion as component of selective phase 188, 189 -, inclusion compounds 202,203 -, methyl-N-xtylglyoximes 196 -, n-nonyl-pdiketonates 197 -, separation of isotope-labelled unsaturated compounds 190-193 -,silver salt 187-191 -,thallium nitrate 193 -,theory of the retention of complex-forming compounds 186,187 -, Werner complexes 196 -,zinc stearates 197 Chemical methods in gas chromatography, see Analytical reaction gas chromatography Derivatization, see Chemical formation of derivatives Determination, acetaldoximes (onti,s y ~ ) 75,77 -, active hydrogen 296 -,acids 29,33,41 - alcohols 36,51, 79 -, aldehydes , s -, alkoxy groups 300 -, alkyl groups 302 -, aluminium 265 -, ammonia 269 -,amines 26,53 -_ ,amino acids 16-18 -,amino groups 297 -, automobile paints 16 -,barbiturates 20,21 -, carbonates 264,265 -, carbon disulphide 269 ,carbon oxides 267,268 -,carboxylic acids 53,54 -,conjugated dienes 72,79 -, degree of crystallinity 130 -, dicyanogen 269 -,ethanol 263,271 312 SUBJECT INDEX -,formic acid 270 germanium alloy 42 , halogens 232,265 homovanillic acid 34 , hydrogen cyanide 269 , impurities, in butadiene 25 ,in carbon dioxdie 256 _ _,-,in ethylene 250 -, _ _,in carbon dioxide 256 -, inorganic acids 54, 55 , inorganic anions 23-25 , inorganic volatile oxidizing agents 269 ,iodide 271 -, isohomovanillic acid 34 ~-, isotacticity 130 ketones , 53 -, magnesium 265 -, mercury 272 ,metals 23, 54, 55, 273 methyl esters of organic acids 117 , microorganisms 18, 119 -, molecular weight 130 morphine alkaloids 28 ~-, natural fibres I17 ,nitrate 271, 272 , nitrogen dioxide 27 I , 278 -, nitrogen-alkyl groups 301 - ,oxygen 273 ~, oxygen-containing groups 298 -., penicillins 21, 37, 38 - , pentadiene 75 -, phenols 41 , phosphates 42,43 ~ ,polyesters 19, 20 , polyethyleneimine 45 , racemates of amino acids 23 -_,rare earth elements 277 -, rubbers 14 -, selenium 273 , silicon-alkyl groups 301 -, steroids 26 , styrene , 4 -, sulphur-alkyl groups 301 , sulphur-containing groups 299 ,synthetic fibres 17 -.-,thymol 29 -.-, tranexamic acid 33 - -, transuranic elements 277 , unsaturated bonds 302 , vanilmandelic acid 34 vinyl groups 302 - vitamin H, 37 - water 258,262-264 Elemental analysis, see Methods of elemental analysis -, ~ ~~ Functional group analysis 287-310 , advantages 287 -, 289-291 289-291 -_,preliminary reaction 288 -, reaction after separation 292 ,-, microscope, crystallographic and colorimetric methods 295 , stage of identification 287 -, use of reaction with heteroatoms reagent 290 -, use of silylation 290 Kinetic chromatographic method, basic arrangements of chromatographic systems 76 -,definition 67 -, differential kinetic method 69-71 -, field of application 69 -, stop-flow method 80 ,tasks 68 -,techniques for studying the kinetics of liquid-phase reactions 73, 74 Kinetic methods, classification 67 -_ , definition 67 Methods of elemental analysis 209 -248 -, advantages 209 -, conditions of determination 212 ,-, flow-through reactor 21 -_ , , stationary 212 -,determination of elements 209, 210 , -, arsenic 232 -,-_ ,calculation method 214,215 -_ , ,carbon 213 _-_ ,-,halogens 232 -,-,hydrogen 213 -, -,in GC separated fractions 233 -, -, in flow of hydrogen 226 -_ , , in flow of oxygen 225 -,-,metals 232 -,-_ ,nitrogen 218, 219 _ ,-,oxygen 229 -, -, phosphorus 232 -_ , ,sulphur 225,228 -,elution analysis 212 -, frontal analysis 12 -, microdetermination 217,218 - ,steps 210 _ _,types of reaction used 210,211 Pretreatment of samples 15-66 -,apparatus used 1,42 -,derivatives 45 -, peculiarities of the elaboration of techniques 30 ~ - see , also Chemical formation of derivatives -, advantage of integrated method 87 -_ d i e c t methods ,indirect methods SUBJECT INDEX Pyrolysis-gas chromatography 85- 138 advantages 85 automatic sample injector 99,100 comparison of commonly used methods 94 -, cross-correlation chromatography 128 -, Curie-point filament 92 -, Curie points of some materials 97 -, Curie-point pyrolysis-mass spectrometry 102 -, definition 85 -, dynamic method 90 -, equipment 89 -, experimental methods 89 -, fingerprint method 88,89 -, gas flow-rate 109 -, hydrogenation pyrolysis 129 -, laser-induced decomposition 102, 103 -, nichrome filament 92 -,optimal combination of peaks 123-125 -, optimal experimental conditions 106 -,plasma stoichiometric analysis 104, 105 -, platinum filament 92 -, pyrolysers with heating chamber 91 -, pyrolysers with heating element 91 -, pyrolysis time 109 -, sample size 108 -, steps of experiments 86 -, temperature 107 -,temperature pattern of sample heating 95, 96 -, thermorefractography 108 -, volatile compounds 120 -, -, -, 31 Sample pre-treatment, see Pretreatment ot samples Stationary phases, chemically selective, see Chemically selective stationary phases Subtraction method 157-184 -, chromatographic schemes 160 ,combination with phase-equilibrium method 163 -,content of the components in the total unresolved peak 160 ,definition 157, 158 -,equation 157 -, molecular sieves as subtraction reagents 164-166 -,reagents 177, 178 -,subtraction of hydrocarbons by chemical sorbents 168 -1 70 -, total unresolved peak 160 - , trace impurity analysis 179 Trace analysis 249-285 -, advantages J 50, 249 -, chemical concentration method 258, 260 -, classification of methods 252, 253 _., frontal chemical concentration 255 ,frontal chemisorptive concentration 256 -, improvement of detection 267 -, method for decreasing the retention time 26 -, method for increasing the retention time 250 This Page Intentionally Left Blank