JOURNAL OF CHROMATOGRAPHY LIBRARY - VOLUME 24 chemical methods in gas chromatography

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 determining a particular class of compound are based on the combined use of GC with mass spectrometry and computers [251,252] The contribution of GC to the functional group analysis of volatile compounds cannot be overestimated Chemicochromatograpliii; methods enable one in virtually all instances to advance from group identification to the identification of individual substances and widen the range of the reactions that yield not only coloured or gaseous compounds, as in classical methods, but any volatile (and sometimes involatile) compounds REFERENCES 305 In summary, some of the most promising trends in functional group analysis can be postulated as follows: (1) the use of capillary chromatography in the functional group analysis of impurities and trace amounts of a compound; (2) the use of combined concentration methods in functional group analysis for analysing impurities in complex samples (analysis of environmental and biological materials, etc.); (3) development of simple and effective procedures of functional group analysis by using reagent vapours in a carrier gas; (4) development of the systematic analysis of functional groups by reaction GC based on the use of highly sensitive selective detectors and corresponding functional group reactions REFERENCES A.N Nesmeyanov and N.A Nesmeyanov, Nachala Organicheskoi Khimii (Basic Organic Chemistry), Khimiya, Moscow, 1974 S.Coffey (Editor), Rodd’s Chemistry of Carbon Compounds, Elsevier, Amsterdam M.F Ansell (Editor), Supplements to Rodd’s Chemistry of Carbon Compounds, Elsevier, Amsterdam S.R Sandler and W Karo, Organic Functional Group Preparations, Academic Press, New York, 1968-1971 A.I Vogel, Practical Organic Chemistry, Longmans, London, 1972 P.G Ashmore, Catalysis and Inhibition of Chemical Reactions, Butterworths, London, 1963 E.A Moelwyn-Hughes, m e Chemical Statics and Kinetics of Solutions, Academic Press, London, New York, 1971 J.A Riddick and W.B Bunger, Techniques of Chemistry, Wiley-Interscience, New York, 1970 V.V Brazhnikov, Differentsialnie Detektory dlya Gazovoi Khromatografii (Differentid Detectors for Gas Chromatography),Nauka, Moscow, 1974 10 M KrejEi and M Dressler, Chromatogr Rev., 13 (1970) 11 J SevEik, Detectors in Gas Chromatography,Elsevier, Amsterdam, 1976 12 E Pungor, K Toth, Z Feher, G Nagy and M Varedi, Anal Lett., (1975) 13 J Gasparic,Advan Chromatogr., (1968) 14 V.S Tatarinsky and V.G Berezkin, in Gazovaya Khromatografiya v Neftekhimii (Gas Chromatography in Petrochemistry), Nauka, Moscow, 1975, p 75 15 T.S Ma and A.S Lades, Organic Functional Group Analysis by Gas Chromatography: Academic Press, London, 1976 16 S Siggia (Editor), Instrumental Methods of Organic Functional Group Analysis, Wiley-Interscience, New York, 1972 17 J.F.M McOniie (Editor), Botective Groups in Organic Chemistry, Plenum Press, New York, London, 1973 A.E Pierce, Handbook and General Gztalog 1979-1980, Pierce Eurochemie, Rotterdam, The Netherlands 19 J.F Klebe, H Finkbeiner and D.M White,J Amer Chem Soc., 88 (1966) 3390 20 J Merr and F Raschdorf, Textilveredlung,7 (1972) 540 21 C.C Sveely, R Bentley, M Makita and W.W Weels,J Amer, Chem Soc., 85 (1963) 2497 22 L.M Andronov and Yu.D Norikov, Zh Anal Khim., 20 (1965) 1007 23 R Kleiman, F.R Earle and LA Wolf,J Amer Chem Soc., 45 (1968) 248 24 G.L Kumari, W.P Collins and I.F Sommoville,J Chromatogr.,4 (1969) 22 25 R.A Gelman and J.R Giebertson, Anal Biochem., 31 (1969) 463 26 E Evrard and F Jansen, J Lipid Res., (1968) 226 306 FUNCTIONAL GROUP ANALYSIS W.H Gutenmann and D.J Lisk, J Agr Food Chem., 13 (1965) 48 A Zlatkis and B.C Pettit, Chromatogmphia, (1969) 484 W.G Galetto, R.E Kepner and A.D Webb, Anal Chem., 38 (1968) 34 P.B Cower and B.C Thomas, J Chromatogr., 44 (1968) 175 G Enlund, B Josefson and C Roos,J Qlromatogr., 142 (1977) 575 H Liliebahl, Acta Chem Scand,, 20 (1966) 95 N.N Mihailovskaya and N.A Deyneko, Tr CIAP, No 13 (1972) 172 Mlejnek,J Chromatogr., 70 (1972) 59 V.N Piyalkin, V.A Samoylov, V.A Latysheva and A.K Slavinskyy, Khim Drev., No 11 (1972) 133 36 M.J Levitt, Anal G e m , 45 (1973) 628 37 D.T.Downing, Anal Chem., 39 (1967) 218 38 J.J Bailey,Anal Chem., 39 (1967) 1485 39 E.D Bitner, A.C Lanser and H.J Dutton, J Amer Oil Chem Soc., 48 (1971) 633 40 J ChuraEek, M Drahokopilova, P.Matousek and K Komarek, Gzromatographia, (1969) 493 41 L Rudlins, WaterRes., (1972) 871 42 M Rogozinski, J Gas Chromatogr., (1964) 605 43 B.S Middleditch and D.M Desiderio, Anal Lett., (1972) 605 44 E.A Crowell and J.F Guymon, Amer Enol Viticult., 20 (1969) 155 45 J.W Schwane and M.N Gilmour, Anal Chem., 41 (1969) 1686 46 F.K Kawahara, Anal Chem., 40 (1968) 2073 47 K Blau, Clin a i m Acra, 27 (1970) 48 R.A Chalmers and R.W.E Watts, Anal.vst (London),97 (1972) 951 49 B.A Davis, P.A Durden, P Pun-Li and A.A Boulton, J Chromatogr., 142 (1977) 517 50 P.H Degen and A Schweizer, J Chrornatogr.,142 (1977) 549 51 R.W Morrow J.A Dean, W.D Shults and M.R Cuerin, J Chromatogr Sci., (1969) 572 52 G Ertingshausen, C.W Gehrce and W Aue,Separ Sci., (1967) 681 53 K Jacob, W Vogt,I Fischer and M.Knedel, Tetrahedron Lett., (1975) 1927 54 W Vogt, K Jacob, Fischer and M Knedel, Anal Chem., 279 (1976) 158 55 K Jacob, C Falkner and W Vogt,J Chromatogr., 167 (1978) 67 56 R.R.Linko,H.KallioandK.Rainio,J Chrornatogr., 155 (1978) 191 57 H KalJio and R.R Linko, Z Lebensm.-(Inters.-Forsch., 153 (1973) 23 58 P.W Lanpvardt, T.J Nestrick, E.A Hermann and W.H Braun, J Chromatogr., 153 (1978) 443 59 V.G Berezkin, G.L Gromova and G.L Golitsina, Vysokomol Soedin., Ser A , 17 (1975) 1177 60 Z Deyl, K Macek and J Jan& (Editors), Liquid Column Chromatography, Elsevier, Amsterdam, 1975 61 S.A Kibardin and K.A Makarov, Tonkosloynaya Khromatografya v Organicheskoi Khimii (Thin-Layer Chromatography in Organic Chemistry), Khimiya, Moscow, 1978 62 Vials and Closures, Pierce, Rockford, IL, 1977 63 Chromatography, Chrompack, Middelburg, 1978, No 64 V.G Berezkin, V.D Lostshilova, A.G Pankov and V.D Jagodovskii, Khromato-raspredelitelnyi Metod (Distribution Orromatography Methods), Nauka, Moscow, 1976 65 R Bassette,C Ozerus and C.H Whitnch, Anal Chem., 34 (1962) 1540 66 B.E Loney, R Bassette and M Ward,./ Dairy Sci., 46 (1963) 922 67 R.Bassette, M.E Turner and M Ward, J Dairy S c i , 49 (1966) 81 68 M Gottauf, Anal Orem., 218 (1966) 175 69 V.G Berezkin, in Trudy Tashkentskoi Konferentsii PO Mirnornu Ispolzovaniyu Atomnoi Energii (Proceedings o f Tashkent Symposium on the Peaceful Utilization of Atomic Energy), Vol 2, Akad Nauk Uzb SSR, Tashkent, 1962, p 425 70 J.E Hoff and E.D Feit, Anal Chem., 35 (1963) 1298 71 J.E Hoff and E.D Feit,Anal Chem., 36 (1964) 1002 72 K.M Frederiks and R Taylor, Anat Chem., 38 (1966) 1961 73 E Kominski, E.W Wasowicz and R Prrybylski, Chem Anal (Warsaw), 17 (1972) 1307 74 J.T Walsh and C Merritt, Anal Chern., 32 (1 960) 1378 27 28 29 30 31 32 33 34 35 REFERENCES 307 75 M.S Vigdergauz, L.V Semenchenko, V.A Ezrets and Yu.N Bogoslovskii, Kachestvennyi Gazokhromatograficheskyi Analyz (Qualitative GQS Chromatographic Andysis), Nauka, Moscow, 1978 76 C.D Chriswell and J.S Fritz, J Chromatogr., 136 (1977) 371 77 D.A Cronin and S Gilbert, J Chromatogr., 71 (1972) 25 78 D.A Cronin and S Gilbert,J Chromatogr., 89 (1974)209 79 M Gine and V Cerda, Analusis, (1975)580 80 B Casu and L Cavaflotti,Anal Chem., 34 (1962)1514 81 J Jan&,J Chromatogr., 15 (1964) 15 82 R Kaiser,Z Anal Chem., 205 (1964)283 83 R Kaiser, in L.S Ettre and W.H McFadden (Editors), Ancillary Techniques of GQSChromatography, Wiley, New York, 1969,Ch 84 J Janik,J Chromatogr., 16 (1964)494 85 P.R Boshoff, B.J Hopkins and V Pretorius,J Chromatogr., 126 (1976)35 86 Yu.E Lille and H.A Kundel, Khimiya i Technologiya Goruchih Slantsev i Productov ikh Pererabotki (Chemistry and Technology of Oil Shale and its Processing Products), Nedra, Leningrad, 1967,No 3, p 254 87 I Lysyj and R.C Greenough,Anal Chem., 35 (1963) 1657 88 E.J Norton, L Turner and D.G Salmon,Analyst (London), 95 (1970)80 89 I Daido, R Takao and T Nobuo, BunsekiKagaku (Jap Anal.), 21 (1972) 367 90 H Roth,Microchernie, 11 (1932)40 91 M.N Chumachenko and L.B Tverdyukova,Dokl Akud Nuuk SSSR, 142 (1962)612 92 M.N Chumachenko, L.B Tverdyukova and F.G Leenson, Zh Anal Khim., 21 (1966)617 93 A.E Mysak, Kandidat i’hesis, Institute of Petrochemical Synthesis, Academy of Sciences, Moscow, 1965 94 Z.A Shevchenko, E.G Rumyantsev, I.A Favorskaya and A.A Nikitina, Vestn Leningr Univ., Fiz., Khim., No (1972)141 95 E Miller (Editor), Houben-Weyl, Methoden der Organischen Chemie, Band II, Anabtische Methoden, 4th (revised) ed., Georg Thieme, Stuttgart, 1953 96 I.V Matveeva, Zh Anal Khim., 27 (1972) 1172 97 E.I Norton, L Turner and D.G Salmon,Anulyst (London), 95 (1970)80 98 V.G Berezkin, A.E Mysak and L.S Polak, Khim Tekhnol Topl MQSd,No (1964) 67 99 V.G Berezkin, A.E Mysak and L.S Polak,Neftekhimiya, (1964) 156 100 I.V Matveeva,Zh Anal Khim., 27 (1972)1177 101 I Franc and F Mikes, Cblfect Czech Chem Commun., 31 (1963) 363 102 I Lisyi and R.C Greenough,Anal Chem., 35 (1963) 1957 103 E.R Hoffman and I Lisyi, Microchern J., (1962)42 104 B.G Belenkii and V.A Orestova, Izv Akad Nauk SSSR, Ser Khim., (1964)182 105 I Susumu, A Satoru and H Tadasi,J Chem Soc Jap., Pure Chem Sect., 91 (1970)251 106 M.V Palyanova, V.S Tatarinskii and M.M Fedyachkin,Zavod Lab., 38 (1972)532 107 H.E Mishmash and C.E Meloan, Anal Lett., (1971)295 108 D.D Van SlykeJ Biof Chem., 22, (1915) 281 109 I Daido, T Taka0 and T Nobuo, Bunseki Kugaku (Jap Anal.), 21 (1972) 363 110 A.T Austin,J Chem Soc., (1950) 149 111 M Schenk, Hoppe-Seyler’sZ Physiol Chem., 286 (1951)270 112 G Kainz, F Kasler and H Huber,Mikrochim Acta, (1959)893 11 S.I Obtemperanskaya and Nguen Dyk Hos, Zh Anal Khim., 24 (1969) 1588 114 Nguen Dyk Hos and S.I Obtemperanskaya, Vestn Mosk Univ., Ser 2: Khim., 13 (1972) 615 115 U Toyozo, N Terimichi and T Ruiji, BunsekiKagaku (Jap Anal.), 21 (1972)993 116 P.A Toseland and P.H Scott, Clin Chim Acta, 25 (1969)75 117 J.S Nooman, P.W Murdick and R.S Ray, J Pharmacol Exp Ther., 168 (1969)205 118 A Zlatkis and B.C Pettit, Chromatographia, (1969)484 119 R.L Tilden and C.H Van Middelam, J Agr Food Chem., 18 (1970) 154 120 J.B Brooks,C.C Alley and J.A Liddie,Anal Gem., 41 (1974) 977 308 FUNCTIONAL GROUP ANALYSIS 121 S Hara and Y Matsushima,J Biocheni (Tokyo), 71 (1972) 907 122 S.W Gunner and R.C O’Brien, J Ass Offic Anal Cheni., 52 (1969) 1200 123 S Baba, I Hashimoto and I Yutaka,J Chromafogr., 88 (1974) 373 124 J.A Lubkowitz, J Chromatogr., 63 (1971) 370 125 P Capelh and E.C Horning,Anal Chem., 38 (1966) 316 126 S Kawai and Z Tamura, Chem Phorm Bull., 15 (1967) 1493 127 T Wall, Acta Pharm Suecica, (1968) 353 128 A Savitsky and S Siggia,Anal Chem., 46 (1974) 149 and 153 129 P Hartvig, J Vessman and A.B Kabi,J Chromatogr Sci., 12 (1974) 722 130 P Hartvig, W Handl, J Vessman and C.M Svahn, Anal Oiem., 48 (1976) 390 131 T Walle,J Chromatogr., 111 (1975) 133 132 J Vessman, P Hartvig and M Mohnder, Anal Left., (1973) 699 133 S.V Vitt, M.B Saporovskaya, G.V Awakuniov and V.M Belikov, Usp Khim., 45 (1976) 548 134 K.V Alekseeva and L.P Hramova, Zh Anal Khim., 27 (1972) 163 135 S.1 Obtemperanskaya and Nguen Dyk Hos, Vestn Mosk Univ., Ser 2: Khirn., 11 (1970) 369 136 C.W Gehrke and K Leiner,J Chromarogr., 53 (1970) 201 137 C.W Gehrke and K Leiner,J clrromatogr., 57 (1971) 219 138 E.D Morgan and C.F Poole,J Chromatogr., 89 (1974) 225 139 W.Aue and S Kapila,J Chromatogr Sci., 11 (1973) 255 140 J.W Blake, R.S Ray, J.S Nooman and P.W Murdick, Anal Chem., 46 (1974) 288 141 G Kubberod, Acta Chem Scand., 26 (1972) 2544 142 S Hywyler, Experientia, 28 (1972) 718 143 T.S Ma, C.T Shang and E ManchqMikrochim Acla, (1964) 571 144 R.C Hall and C.S Giam,Anal Chem., 42 (1970) 423 145 J.N Whyte and J.R Engler, Anal Biochem., 59 (1974) 426 146 M.V Palyanova, V.S Tatarinskii and M.M Fedyachkin, Zavod Lab 39 (1973) 545 147 H Tadshi and I Susumu, Bull Chem Soc Jap., 44 I 1971) 2427 148 V.M Nevskii, V.G Gutsalyuk, L.G Grabarik and A N Svetov, Izv Akad Nauk Kaz SSR Ser Khim., (1967) 27 149 A Shun, H Toshiyuki and S Kazuo,Bunseki Kagaku (Jap Anal.), 21 (1972) 1389 150 H.M Fales and T Luukkainen, Anal Chem., 37 (1965) 955 151 Mlejnek,J Chronzarogr., 70 (1972) 59 1.52 H.P Klemm, U Hintze and G Gercken,J Cliromatogr., 75 (1973) 19 153 R.H GreeIey,J Chrornatogr., 88 (1974) 229 154 J.B Brooks, C.C Alley and J.A Liddle, Anal Chem., 46 (1974) 1930 155 B.S Middleditch and D.M Desiderio, Anal Leu., (1972) 605 156 J.P Thenot, E.C Horning, M Steffard and M.G Horning, Anal Lett., (1972) 217 157 R.D Stevens and C.H Middelcm, J Agr Food Chem., 14 (1966) 149 158 P Rokainen, S Brumnier and H Suomalainen,J Chromatogr,, 28 (1967) 253,270 and 443 159 J.C Shogt, P.H Bagemann and J.H Rec0urt.J Lipid Res., (1961) 142 I60 S Harrison, Analyst (London) 92 (1967) 773 161 D.G Carlson and W.H TaUent,J Chromatogr Sci., (1970) 276 162 M.G Horning, E.A Boucher A.M Moss and E.C Homing, Anal Lett., (1968) 713 163 R.J Soukup, R.J Scarpellino and E Danielczk, Anal Cheni., 36 (1964) 2255 164 R.E Leonard and J.E Kiefer, J Gas Chromatogr., (1966) 142 16.5 H Springler and F Mackert, Mikrochim Acta, (1959) 122 166 W.A Schoeder, J Cua, G Matsud and W.D Fenninger, Biochim Biophys Acta, 63 (1962) 32 167 D.N Ward and J.A Coffey,Biochemisrry, (1964) 1575 168 D.N Ward, J.A.Coffey,D.B Ray andW.M Zamkin,Anal Biochem., 14 (1966) 243 169 V.S Kabanov and M.N Chumdchenko, Sh Nauchn Rah Vsey Nauchnoissled Itits Lek Rast., No (1970) 200 1I M.N Chumachenko and V.S Kabanov, Sbornik Prohlem.v Ana1,vricheskoi Khimii, Nauka, Mosmw, 1970, No 1, p 52 REFEREKCES 309 171 L.P Atkinson and G Natoli,Anal Chem., 46 (1974) 1316 172 A.S Prochuhan, E.M Barnovskaya, G.M Bikulatova and R.V Zainullina, Zh Anal Khim., 24 (1969) 1261 173 F.K Kawahara,Anal Chem., 40 (1968) 1009 174 I Susumu and H Tadash,J Chem Soc Jap., Pure C'hem Sect., 90 (1969) 1027 175 S Siggia, L.R Whitlock and J.C Tao, Anal Chem., 41 (1969) 1387 176 S Siggia and L.R Whitlock, Anal Chem., 42 (1970) 1719 177 L.R Whitlock and S Siggia, Separ PuriJ Methods, (1975) 299 178 A.N Kozlov and A.A Sptyskov, Izv Vyssh Uchebn Zaved Khim Khim Tekhnol., 13 (1971) 1752 179 J.J Kirkland, Anal Chem., 32 (1960) 1388 180 J.B Himes and I.J Dowbak,J Gas Chromatogr., (1965) 194 181 J.S Parsons,J Chromafogr Sci., 11 (1973) 659 182 J.S Parsons,J Gas Chromatogr., (1967) 254 183 P.C Rahn and S Siggia, Anal Chem., 45 (1973) 2336 184 S Zeisel and R Fauto, Anal Chem., 42 (1903) 549 185 G Castello,J Chromatogr., 41 (1969) 313 186 S Vertaller and F Martin, Chim.A n d (Paris), 40 (1958) 90 187 J Haslam, J.B Hamilton and A.I Jeffs, Analysf (London), 83 (1958) 66 188 H.J Wesselman,J Amer Pharm Assoc Sci Ed., 49 (1960) 320 189 K Kratzl and K Grubor,Monatsh C'hem., 89 (1958) 618 190 D.Z Miller, E.P Samsel and J.G Cobler, Anal Chem., 33 (1961) 677 191 W.H Gutenmann and D.J Lisk,J Agr Food C'hem., 11 (1963) 470 192 M Tetsuo and K Jukiko,Microchem J., (1963) 141 193 F Ehrenberger,Z Anal Chem., 210 (1965) 424 194 I Klesment and A Kasberg,Mikrochim Acfa, (1967) 1136 195 A.A Karshinin,Zh Anal Khim., 23 (1968) 1072 196 K Nabu and M Tachan,EunsekiKagaku (Jap A n d ) , 17 (1968) 1102 197 A Sun, S Sigemaka and K Masaru,Eunseki Kagaku (Jap Anal.), 18 (1969) 609 198 L.V Kolesnik and M.N Chumachenko, Izv Akud Nauk SSSR, Ser Khim., (1969) 2107 199 A Kogerman, A Kongas and Kirret, Izv Akud Nauk Est SSR, Khim., Geol., 22 (1973) 274 200 M.N Chumachenko and L.V Kolesnik,lzv Akad Nauk SSSR, Ser Khim., (1971) 2090 201 M.M Schachter andT.S Ma,Mikrochirn Acta, (1966) 55 202 C.V Viswanathan, J Chromatogr., 98 (1974) 129 203 D.G Anderson, K.E Isakson, D.L Snow, D.J Tesari and J.T Vandeberg, Anal C'hem., 43 (1971) 894 204 M.N Chumachenko and L.V Kolesnik, Izv Akad Nauk SSSR, Ser Khim., (1978) 1874 205 S.P Francoski and S Siggia, Anal Chem., 44 (1972) 507 206 C.L Hanson and R.C.Smith, Anal Chem., 44 (1972) 1571 207 J Franc and K Placek,J Chromatogr., 67 (1972) 37 208 V.M Krasikova, V.P Milashkevich and A.N Kaganova, Zh Anal Khim., 29 (1974) 1199 209 H Jachinand J.M Slanski,AnaZ Chem.,42 (1970) 801 210 H Tai, R.M Powers and T.F Protzman, Anal Chem., 36 (1964) 108 21 A Sune, S Sigetaka and K Masaru, Bunseki Kagaku (Jap Anal.), 19 (1970) 488 212 A Campiglio, Farmuco, 28 (1973) 31 213 J Franc, J Dvoracek and V Kolouskova,Mikrochim Ichnoanal Acta, (1965) 214 J Franc and J Dvoracek,J Chromatogr., 14 (1964) 340 215 J Franc and K Placek,J Chrornatogr., 48 (1970) 295 216 V.M Krasikova, A.N Kaganova and V.D Lobkov,Zh Anal Khim., 26 (1971) 1635 21 I B.M Luskina and E.V Terentyeva, Funktsioriahy Analys Krernniorganicheskih Soedinenii Metodom Gazovoi Khromatografii, NIITEKhim, Moscow, 1977 218 J Franc and K Placek, J Chromatogr., 67 (1972) 37 219 J Franc, J Senkvrova, F Mokes and K Placek,J Chromatcgr 43 (1969) 220 S.P Evdokimova, N.A Isakova and V.F Evdokimov, Zh Analyt Khim., 26 (1971) 806 221 E.R Bisseland D.B Fields,J Chromatogr Sci.,10 (1972) 164 310 FUNCTIONAL GROUP ANALY SlS J Franc, Czech, Pa?., 139,431 (1970) K.H Nelson, W.J Hines, M.D Grimes and D.E Smith, Anal Chem., 32 (1960) 1110 F Drawert, R Felyenhauer and G Kupfer, Angew Chem., 72 (1960) 555 F Drawert and K.H Reuther, Chem Ber., 93 (1960) 3066 R.W Dunning and J.A Leonard, Chromatographiu, (1969) 293 M Beroza and R Sarmiento, Anal Chon., 38 (1966) 1042 A Ivanov and Eisen,J Chromatogr, 69 (1972) 53 B Hallgren and S Larsson, Acta Ozem Scand., 17 (1969) 1822 T.L Mounts and H.J Dutton, Anal Chem., 37 (1965) 641 A.J.FulioandJ.F.Mead,J Bwl Chem.,234(1959) 1411 D.F Keumme1,Anal Chem., 36 (1964) 426 M.D Bon, Uch Zap Leningr Gos Univ., Ser 111,(1938) W.A Bouner, J Chem Educ., 30 (1953) 452 M Beroza and B.A Bierl, Anal Chem, 38 (1966) 1976 M Beroza and B.A Bier1,Mikrochim Acra, (1969) 720 B Smith, R Ohlson and A.M Ohlson, Acta Chem Scand., 16 (1962) 1463 M Beroza and B.A Bierl, Anal Chem., 39 (1967) 1131 V.Z Davison and H.J Dutton, Anal Chem., 38 (1966) 1302 R.A Stein, J Amer Oil Chem Soc.,41 (1965) 325 B.R Moore and W.V Brown,J Chromatogr., 60 (1971) 157 E.C Nickelland 03.Privett, Lipids, (1966) 166 0,s.Privett and E.C Nickell, J Amer Oil Chem SOC.,43 (1966) 393 R.A Stein and N Nicolaides, J Lipid Res., (1962) 476 E.R White, B.M Sutton, J.E Blank, E Moeckel and J.E Zarembe, Anal Chem., 44 (1972) 1582 246 M.S.B Munson, Anal Chem., 43 (1971) 28A 241 D.F Hunt, Finnigan Specrra, 6, No (1976) 248 D.F Hunt, C.N McEven and R.A Upham, Anal Chem., 44 (1972) 1292 249 D.F.Hunt,Advan MassSpectrom.,7 (1974) 517 250 D.F Hunt and J.F Ryan,J Chem Soc Chem Commun., (1972) 620 25 N.A.B Gray and T.O Gronneberg,AnaZ Chem., 47 (1975) 419 25 T.O Gronneberg, N.A.B Gray and G Eglinton, Anal Chem., 47 (1975) 415 25 W Diinges, Pra-chromatographische Mikrornerhoden, Huthig, Heidelberg, Basel, New York, 1979 254 R Liardon and K Kiihn, J High Resolut Chromatogr Chromatogr Commun., (1978) 47 255 E Janos, J Balla, E Tyihak and R Gaborjanyi,J Chromatogr., 191 (1980) 239 25 S Yamamoto, K Kakuno, S Okahara, H Kataoka and M Makita, J Chromatogr., 194 (1980) 399 25 U Hannestad and B Sorbo,J Chromatogr., 200 (1980) 171 258 E Reiner, Nature (London), 206 (1965) 1272 259 J MacCee, J Gas Chromatogr., (1968) 48 260 L.V Andreev and A.N Sklifas, Izv Akad Nauk SSSR, Ser Bzol., No (1979) 95 261 L.V Andreev, M.A Bobyk and A Guelin, C.R Acad Sci., Ser D ,288 (1979) 173 262 R.J Williamsand S Siggia,Anal Chem.,49 (1977) 2337 263 D.D Schlueter and S Siggia, Anal Chem., 49 (1977) 2343 64 D.D Schiueter and S Siggia,Anal Chem., 49 (1977) 2349 265 G.W Francis and T Tande, J CRromutogr., 150 (1978) 139 266 S Honda, Y Fukuhara and K Kakehi, Anal Chem., 50 (1978) 55 267 C.F Poole and A Zlatkis, J Chromatogr., 184 (1980) 99 268 T.I Poznyak, D.M Lisitsyn, F.S Dyachkovsky and S.D Razumovsky, Zh Anal Khim., 32 (1977) 783 26 H Ehrsson, Acta Pharm Suecica, (1971) 113 70 J.P Thenot, E.C Horning, M Stafford and M.C Horning, Anal Lett., (1972) 217 27 C.A Burkhard, J Org Chem., 22 (1957) 592 222 223 224 25 226 227 228 229 30 231 232 233 234 235 236 237 238 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