Practical Supercritical Fluid Chromatography and Extraction

455 Pages·2017·19.414 MB·English

by  Raymond Bonnett, Caudell Caudell

Practical Supercritical
Fluid Chromatography and
Extraction
Chromatography: Principles and Practice
This book series will be a multi-volume, comprehensive treatise on chromatography to
meet the requirements of chromatographers and nonspecialists who need to understand
and use chromatography.
Edited by B. Ravindranath, Bharavi Laboratories Ltd., Bangalore, India
Volume 1
Structure and Retention in Chromatography: A Chemometric Approach
Roman Kaliszan
Volume 2
Practical Supercritical Fluid Chromatography and Extraction
edited by Marcel Caude and Didier Thiebaut
Other Volumes in Preparation
Planar Chromatography (TLC) - Handbook of Thin Layer Chromatography
edited by E. Soczewinski
Chromatographic Separation of Carbohydrates
edited by S. Churms and A. Stephen
Chromatographic Separation of Lipids
edited by A. Kuksis
This book is part of a series. The publisher will accept continuation orders which may
be cancelled at any time and which provide for automatic billing and shipping of each
title in the series upon publication. Please write for details.
Practical Supercritical
Fluid Chromatography and
Extraction
Edited by
Marcel Caude and Didier Thiébaut
Centre National de la Recherche Scientifique
Laboratoire Environnement et Chimie Analytique
Ecole Supérieure de Physique et de Chimie Industrielles de la Ville de Paris
France
harwood academic publishers
ah p«
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Malaysia • The Netherlands • Russia • Singapore • Switzerland
Copyright © 1999 OPA (Overseas Publishers Association) N.V. Published by license under
the Harwood Academic Publishers imprint, part of The Gordon and Breach Publishing
Group.
All rights reserved.
No part of this book may be reproduced or utilized in any form or by any means, electronic
or mechanical, including photocopying and recording, or by any information storage or
retrieval system, without permission in writing from the publisher. Printed in Singapore.
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British Library Cataloguing in Publication Data
A catalogue record for this book is available from the British Library.
Practical supercritical fluid chromatography and
extraction. - (Chromatography : principles and practice ;
2)
1. Supercritical fluid chromatography
I. Caude, Marcel II. Thiebaut, Didier
543'.0896
ISBN: 90-5702-409-8
Contents
Preface to the Series Vll
Preface ix
Contributors xi
1 Properties of Supercritical Fluids Relevant to Extraction and Chromatography 1
A.A. Clifford
2 Packed Colunms in SFC: Mobile and Stationary Phases and Further
Requirements 15
H.-G. Janssen and X. Lou
3 Capillary Column SFC and Requirements 53
M.W. Raynor, V. Sewram and M. Venayagamoorthy
4 Instrumentation For SFC and SFE 107
T. Berger and T Greibrokk
5a Detection in SFC 149
D. Thiebaut
5b Supercritical Fluid Chromatography/Mass Spectrometry 161
J.D. Pinkston
5c On-line Capillary Supercritical Fluid Chromatography with Fourier
Transform Infrared Spectrometry Detection 179
Ph. Morin
5d Evaporative Light Scattering Detection in SFC 201
M. Lafosse
6 Principles and Practice of Analytical SFE 219
S.B. Hawthorne and J.W. King
1 Hyphenated Systems in which Supercritical Fluids Play a Key Role 283
P. Sandra, A. Kot, A. Medvedovici and F. David
8 SFC of Drugs and Related Compounds 321
N. Bargmann-Leyder and M. Caude
9 Applications of SFC in the Petroleum Industry 371
E. C. Robert
VI Contents
10 Preparative SFC: Basics and Applications 397
R.-M. Nicoud, J.-Y. Clavier and M. Perrut
Index
General 435
Compound 439
Preface to the Series
Chromatography is well known to all practising chemists and biochemists as a powerful
laboratory technique for separation and qualitative and quantitative analysis. However, it
is not generally recognised what the underlying physicochemical principles are, how
versatile the technique is, and how varied its applications. Over the past half century,
chromatography has become an indispensable tool in several fields of science and tech­
nology. Indeed, it has changed the course of development of many of these fields, including
biology, medicine and chemical technology. The same is true of progress in natural
products chemistry, where developments in chromatography have directly contributed to
exponential growth of the number of new chemical entities isolated and identified. The
role of chromatography in analytical quality control and ecological sciences is well
recognised. Biotechnology is another field which acutely depends on chromatography for
its success; this is because biotechnological processes often yield complex mixtures of very
closely related products and, the availability of efficient separation processes is a limiting
factor in the successful use of the process.
The versatility of chromatography as a separation and analytical technique is immense.
All types of compounds, from the small hydrogen and helium molecules to large and
complex protein molecules, can be separated by chromatography. It is not exaggerated to
state that there are no two compounds, however similar in structure (even optical isomers),
which cannot be separated by one chromatographic technique or another. The tools avail­
able range from a simple laboratory microslide to the most sophisticated automated
instrument and the methods, ranging from liquid-liquid partition to molecular recognition,
are unlimited. Presumably no other technique also offers a range in scale of operation from
attogram to gigagram!
Because the applications of chromatography are so important and varied, commercia­
lization of the technique is inevitable and certainly welcome. The contribution of instru­
ment companies to the development of chromatography is noteworthy. Separation efficiencies
of over a million theoretical plates and detection limits down to g (a single molecule!)
have become possible due to advancements in instrumentation. Several instrument com­
panies have brought out recipe-book type manuals to enable the customers to use instru­
ments and techniques without having to go into the basic principles. While this has served
the user of chromatography in routine analytical laboratories, it has also hampered the
development of the subject: the technique is seldom developed by the user, and as a
consequence is not always tailor-made for a certain application. Solutions to newer sep­
aration problems require clear understanding of the basic principles as well as an overview
of the options available. A prerequisite for this is easy access to structured information.
The purpose of this series is to provide this information.
The subject of chromatography is too diverse and multi-faceted to be adequately pre­
sented by one or two authors in a single work. The structure of the series guarantees a
Vll
vili Preface to the Series
comprehensive, well-balanced coverage of the theory, principles, methodology, instrumen­
tation, practice and applications (both by class of compound and fields of application) of
chromatography. However, each volume in this series can be read as a stand-alone book.
It is a pleasure to acknowledge the co-operation and support of the authors and editors
of the individual volumes and the editorial staff of Harwood Academic Publishers.
B. Ravindranath, Ph.D.
Preface
Nowadays, analytical researchers are faced with increasingly difficult separation problems.
There is a general trend to improve separation techniques for both sample treatment and
analysis to make them shorter and more selective.
It is therefore not surprising that analysts are aware of the fascinating power of supercritical
fluids for extraction and chromatography. Supercritical fluid chromatography (SFC) and
extraction (SFE) involve fluids with low viscosities and high diffusivities, and with a
liquid-like solvent strength, while both gas and liquid chromatography detectors can be
used. Moreover, supercritical fluids offer a unique versatility for controlling chromato­
graphic and extraction selectivity, as their solvating power can be adjusted via pressure
and temperature. High diffusivity entails better kinetics than HPLC: in SFC, efficiency
per unit of time is higher whilst the analysis time is shorter. In SFE, sample penetration
and solute extraction are faster, compared to liquid extraction. Nowadays, these are key
points in analysis, as sample preparation is the most time-consuming step in a separation
process for quality analysis. This is one of the reasons why this book deals with both SFC
and SFE.
A great effort has been made by all the contributors to summarize the best features of
SFC and SFE in their field in such a way that the book remains practical; the general
organization of the book reflects the will to cover the main aspects of the use of SFs in
chromatography and extraction.
Chapter 1 presents in a very concise form the fundamental properties of the supercritical
fluids that make them relevant for chromatography and extraction.
Chapters 2 and 3 deal with the choice of colunms (packed or capillary) and stationary
phases to be used in SFC; in both cases, some applications have been selected by the
authors to highlight the best features of SFC.
Chapter 4 is devoted to SFC and SFE instrumentation, whilst theoretical and practical
aspects of detection are discussed extensively in Chapter 5; special attention has been paid
to the coupling of SFC with mass spectrometry, Fourier transform infrared spectrometry
and light scattering detection.
Analytical SFE principles and applications have been gathered in a unique chapter (#6)
to provide a concise overview of this technique while hyphenated systems in which SFs
play a key role are included in Chapter 7.
The last part of the book deals with several very active applications of SFC. Chapter
8 is devoted to the separation of drugs, including chiral compounds; for these separations
SFC expands the field of application of other separation techniques tremendously.
Chapter 9 gathers the features of SFC in the field of separation of petroleum compounds
and related products; this technique is very relevant for this type of application, owing
to the polarity of the compounds to be separated and the possibility of using gas chro­
matography detectors.
IX