Stationary Phases in Gas Chromatography

JOURNAL OF CHROMATOGRAPHY LIBRARY

Stationary Phases in Gas Chromatography

Harald Rotzsche

HÜLS Aktiengesellschaft, Zentralbereich FE, Marl, F.R.G.

ISSN  0301-4770

Volume 48 • Number Suppl (C) • 1991

Table of Contents

Cover image

Title page

Front Matter

Stationary Phases in Gas Chromatography

Copyright page

Journal of Chromatography Library

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Preface

Chapter 1: Introduction

Chapter 2: Basic Concepts

2.1 Basic Components of a Gas Chromatographic System

2.2 Raw Data Measured from the Chromatogram

2.3 Derived Basic Chromatographic Parameters

2.4 Flow of Gases in a Gas Chromatographic Column and Formation of Bands

2.5 Thermodynamic Bases of Gas Chromatography

2.6 The Quality of Chromatographic Separation

2.7 The Time of Analysis

2.8 Definitions of Symbols Used (Table 1) and List of Essential Relationships (Table 2)

Chapter 3: The Chromatographic Column

3.1 Packed Columns

3.2 Micro-Packed Columns

3.3 Open-Tubular Columns

3.4 Properties and Comparison of the Main Column Types

Chapter 4: Characterization of Stationary Phases

4.1 Intermolecular Forces

4.2 Quantities for the Description of Interactions

Chapter 5: Solid Stationary Phases

5.1 Classification of Adsorbents

5.2 Carbon Adsorbents

5.3 Boron Nitride and Molybdenum Disulphide

5.4 Adsorbents with Hydroxylated and dehydroxylated Surfaces

5.5 Porous Organic Polymers

5.6 Substances Forming Inclusion Compounds*)

5.7 Modified Adsorbents

Chapter 6: Chemically Bonded Stationary Phases

6.1 Adsorbents for Bonding Reactions

6.2 Bonding Reactions

6.3 Properties and Characterization of Chemically Bonded Phases

6.4 Outlook and Prospects for Chemically Bonded Phases

Chapter 7: The Solid Support

7.1 The Particle Size and Shape

7.2 The Surface Area

7.3 Activity of the Original and of the Coated Solid Support

7.4 Diatomite Supports

7.5 Synthetic Silica-based Supports (Volaspher and Quartz)

7.6 Silica Gel

7.7 Micro Glass Beads and Porous Layer Beads

7.8 Fluorocarbon Supports

7.9 Other Support Materials

Chapter 8: Liquid Stationary Phases

8.1 General Properties of Liquid Stationary Phases

8.2 Hydrocarbons

8.3 Silicones

8.4 Alcohols, Ethers and Carbohydrates

8.5 Esters

8.5.4 Acetates, Citrates

8.5.5 Polyesters

8.6 Nitrites and Nitrile Ethers

8.7 Nitro Compounds

8.8 Amines

8.9 Amides

8.10 Heterocyclics

8.11 Sulphur Compounds

8.12 Fluorine Compounds

8.13 Fatty Acids and their Salts

8.14 Salts

8.15 Chiral Stationary Phases*)

8.16 Liquid Crystals*)

8.17 Mixed Stationary Phases

Chapter 9: Selection of Stationary Phases

9.1 General Recommendations for Choosing a Suitable Stationary Phase

9.2 Choosing Stationary Phases for Special Separation Problems with Regard to the Desired Selectivity

9.3 Preferred Stationary Phases

9.4 Approaches to Stationary Phase Selection

Literature

Author Index

General Subject Index

Stationary Phase Index

Front Matter

JOURNAL OF CHROMATOGRAPHY LIBRARY – volume 48

Stationary Phases in Gas Chromatography

Harald Rotzsche

HÜLS Aktiengesellschaft, Zentralbereich FE, Marl, F.R.G.

Amsterdam – Oxford – New York – Tokyo 1991

Copyright page

This book is distributed in all non-socialist countries by

ELSEVIER SCIENCE PUBLISHERS B.V.

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Distributors for the United States and Canada:

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Library of Congress Cataloging-ln-Publication Data

Rotzsche, Harald.

Stationary phases in gas chromatography / Harald Rotzsche. 424 p. 16,5 × 24,0 cm. – (Journal of chromatography library; v. 48)

Includes bibliographical references and index.

ISBN 0-444-98733-9

1. Gas chromatography. 2. Stationary phase (Chromatography)

I. Title. II. Series.

QD79.C45R673 1990

543′.0896-dc20

90-3962

CIP

ISBN 0-444-98733-9 (Vol. 48)

ISBN 0-444-41616-1 (Series)

© Akademische Verlagsgesellschaft Geest & Portig K.-G., Leipzig, 1991

Licensed edition for Elsevier Science Publishers B.V., 1991

All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior written permission of the copyright owner.

Printed in Germany

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.

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Preface

Essen, October 1989, Troisdorf, March 1991

Harald Rotzsche

Every chemist is regularly confronted with samples of which the composition, purity, or concentration of by-products or impurities should be determined, and he/she will have to find the most appropriate analytical method. For volatile or vaporizable constituents of the sample, gas chromatography will often be the method of choice. However, like with any other physical method, reliable results can only be obtained when sufficient knowledge of the potential and limitations of the technique is available.

The analytical result is influenced primarily by the heart of the gas chromatograph, i.e., by the separation column and the stationary phase, and the analyst has to decide carefully which column type and stationary phase to select for the problem at hand. One of the aims of this book is to make the chemist familiar with the numerous stationary phases and column types, with their advantages and disadvantages, to help him/her select the most suitable phase for the type of analytes, and to give him/her detailed information on the chemical structure, physico-chemical behaviour, experimental applicability, physical data of liquid and solid stationary phases and solid supports, which otherwise could only be collected with difficulty from various treatises, handbooks, prospectuses and scientific papers.

To understand the processes occurring in the separation column and to offer a manual both to the beginner (for whom a synopsis on practical and theoretical principles could be of help) and to the seasoned chromatographer (for whom it is convenient to have basic equations and physical correlations at hand), one chapter in this book is devoted to basic theoretical aspects. Further, as the effectiveness of the stationary phase can only be considered in relation to the column type, a chapter on different column types and the arrangement of the stationary phase within the column is included.

Another aim of this book is to stimulate the development of new and improved standardized stationary phases and columns, in order to improve the reproducibility of separations, as well as the range of applications.

This book is also intended for physical chemists, who do not normally deal with chromatography. They can find suggestions for and references to physico-chemical investigations by gas chromatography, particularly in the field of intermolecular interactions and surface studies.

It is always risky to write a monograph on a rapidly expanding field-one only needs to think of the development of fused-silica columns and of cross-linked stationary phases and the rapidly growing amount of relevant literature during the last years. Therefore, I hesitated for quite some time to follow the suggestion made some 10 years ago by Professor J. F. K. Huber of the University of Vienna, whom I thank kindly for his proposal and confidence, to write a book on stationary phases in gas chromatography. On the other hand, this task seemed to be attractive, because in our institute and in our chemical plants we have had to deal with problems of stationary phases since our first gas chromatographic separations in 1957, as the samples to be analysed often comprised low- and very-high-boiling, reactive, even offensive, and/or instable compounds. Therefore, we had to develop stationary phases which would withstand such heavy strains and hence we gained quite a lot of experience in synthesizing, evaluating and applying stationary phases.

This book is not intended to be a review but rather a working instrument. The literature has been critically evaluated and cited only to a limited extent (which is nevertheless quite comprehensive)

I tried to adhere to a systematic representation and nomenclature as far as possible; however, some deviation is intended to serve a better understanding. The order in which the stationary liquid phases are presented may appear to be arbitrary. Except for the hydrocarbons, which are discussed first because of their use as reference liquid phases, the order only indicates to some degree the importance and frequency of application of the phases.

Many of the product names, registered designs and patents referred to in this book are in fact registered trademarks or proprietary names even though specific reference to this fact is not made in the text. Therefore, the appearence of a product name, to simplify matters usually without designation as proprietary, is not to be interpreted as a representation by the publisher and the author that it is in the public domain.

Any book devoted to a specific scientific area is based on the theoretical and experimental efforts of not only the author, but also his teachers, colleagues and co-workers. I shall always gratefully remember Professor Richard Miiller and the late Professors K. Schwabe and A. Y. Kiseleu for their scientific style which I had the opportunity and pleasure to get acquainted with during the years of collaboration and which had a great influence on so many chemists. It is a pleasure for me to acknowledge the contributions of and helpful discussions with Professor W. Engewald, Dr. J.Porschmann and Dr. D. Glindemann. With gratitude I acknowledge the experimental assistance, in some cases lasting for decades, by my co-workers and colleagues in- and outside of my former department. I only mention here H. Hahnewald. W. Schwenke, J. Grasshog Dr. K. -D. Miiller, S. Langer, Dr. J. Schlapa and H. Steimann. In addition, the service of the technical information staff, especially of the scientific libraries of the Chemical Works Nunchritz and Pharmaceutical Works Dresden, and the diligent typing of the manuscript by the two secretaries, Mrs. K. Weisse and Mrs. K. Kurowski, is gratefully acknowledged.

My particular appreciation is due to the publishers for their patience, for the linguistic revision and for the really pleasant cooperation. I wish to thank Huls AG for their support during the final phase of completing this book and Chemical Works Nunchritz for their consent to the publication.

Finally, I would like to express particular thanks to my wife, who by her undertaking of many duties and by her patience and understanding made it possible to write this book.

1

Introduction

Hardly another field in analytical chemistry has devoloped during the past 30 years as rapidly as chromatography. The success of this method is due to its extraordinary performance with regard to separation efficiency and speed. Chromatography enables the analytical chemist to determine the composition of complicated mixtures consisting of individual compounds. At first sight, the principle is relatively simple.

In a chromatographic column or bed, repeated transitions of the constituents to be separated take place between two phases, one of which is stationary, has a large surface and retains the compounds more or less, and the other is mobile and carries the compounds along the stationary phase. Provided that the kind or degree of interactions between the individual constituents and an appropriate stationary phase are different, they undergo different retardations in their transport with the mobile phase in a sequence of dynamic solution or/and adsorption equilibria. Although the entire chromatographic process involves sorption equilibration in addition to convective transport and diffusion, the separation is essentially determined by the first of these three terms, resulting in differences in the distribution ratios between both the phases. In gas chromatography, the mobile phase is a gas, thus having a high diffusion coefficient, and the interaction between molecules and the influence of the nature of usually applied gases, if any, on the distribution ratio is very low. This is the reason why selecting the most appropriate stationary phase is especially important in gas chromatography, whereas in liquid chromatography the distribution ratio, i.e., the separation, can be influenced by both the phases. Here the analytical chemist has a further variance: he can select a suitable stationary phase as well as an appropriate mobile phase, which may be varied between non-polar and strongly polar liquids and liquid mixtures.

If we return to gas chromatography, the separation occurs in a column, and the sample components must be sufficiently volatile at the column temperature in order to be transported by the carrier gas, i.e., by the mobile phase. Owing to the retardation by the stationary phase, the individual components move with different velocities through the column, and separate bands develop, which are detected, characterized and measured at the column outlet.

Depending on the type of column (packed column, packed capillary or microcapillary column, wall-coated open-tubular column) the stationary phase can be an adsorbent, a solid support impregnated with a liquid phase, a thin film of a liquid phase distributed on the inside wall of a capillary tube or a porous layer on the inside wall of the open tube, coated with a liquid phase. As the separability of mixtures is essentially controlled by sorption and desorption processes of its constituents in the interface of the mobile and stationary phases, numerous conditions, in addition to the temperature and the carrier gas flow-rate, have to be considered and optimized, e.g., the particle size and its distribution, the pore size and pore-size distribution of the solid support, the type of adsorbent and liquid stationary phase, viscosity, film thickness and interaction forces of the liquid phase. Such practical aspects of stationary phases in gas chromatography will be emphasized in detail in this book.

2

Basic Concepts

The reader of this book is assumed to be familiar with gas chromatography. Nevertheless, some basic principles, both theoretical and practical, are outlined in this chapter and are intended to provide sufficient help for the beginner and to constitute a useful review for the advanced gas chromatographer. On the other hand, they are not considered to replace a gas chromatographic textbook, and much less are they to enable an excursion into complex gas chromatographic systems or theories.

It seems useful, to start with a general definition of the topic. Beginning with chromatography as the general term, one can define it as the mass transport through a two-phase system being selective for mass transfer. The mass transport is effected by the relative movement of the phases, one of which is compact and the other fluid. [1]. Gas chromatography, as a special kind of chromatography, can be characterized as follows: Gas chromatography, abbreviated to GC, comprises all chromatographic methods in which the moving phase is gaseous. The other phase is stationary and may be either a dry, granular solid or a liquid supported by the granules or by the wall of the column, or both. Separation is achieved by differences in the distribution of the components of a sample between the mobile and stationary phases, causing them to move through the column at different rates and from it at different times. [2].

The following sections of this chapter go into detail and contain the most important relationships applicable in gas chromatography.

2.1 Basic Components of a Gas Chromatographic System

Most gas chromatographers have applied the elution method because of its advantages over other gas chromatographic techniques (e.g., frontal analysis, displacement analysis, vacanto chromatography). Because of their minor importance, these special techniques are not discussed here. The elution technique, introduced into gas chromatography by Cremer [3], is characterized by a continuous flow of the mobile phase through the column, in which the separation of the components of a sample takes place. The individual constituents, together with the mobile phase, leave the column at different times and are detected by a sensitive detection system, which records their concentration in the mobile phase as a function of time, c = f(t), elapsed between sample injection and emergence at the end of the column. The time corresponding to the concentration maximum of a component is its retention time.

A diagram of a gas chromatograph is shown in Fig. 1. The essential part of any gas chromatograph is the column (C), which contains the stationary phase. The carrier gas (G) represents the mobile phase and is generally delivered from a gas cylinder containing the compressed gas. Constancy of the flow-rate is achieved by a flow controller (F), and the flow-rate is measured by a flow meter. An injection system (I) preceding the column permits the sample to be directly introduced and vaporized in the gas stream. The column is followed by a detector (D), in which the separated sample constituents produce electrical analogue signals. After passing an amplifier, in the case of ionization detectors, these signals are displayed on a strip-chart recorder (R), resulting in chromatograms showing individual peaks if the separation was successful. In modern and more expansive apparatus, the detector/amplifier is connected via an analog-digital converter to a more or less sophisticated data system (S), processing two types of data: the already mentioned retention times, which are used for component identification, and the signal intensities (connected with the amounts of the sample constituents passing the detector), which are utilized, after detailed calibrations, for the determination of the concentrations of the components present in the original sample. Devices for temperature control, frequently with a temperature programmer, and measurement are symbolized by (O).

Fig. 1 Diagram of gas chromatograph.

G compressed gas cylinder containing the carrier gas; CG carrier gas cleanup; F flow controller, including flow meter; I injection system; C column; D detector, including supply and amplifier; R recorder; S data system, including interface, integrator and computer; 0 column oven, including temperature control, measure and programmer

2.2 Raw Data Measured from the Chromatogram

Although rather simplistic, it may be useful to specify the raw experimental data resulting directly from the gas chromatogram. Fig. 2 shows a one-component chromatogram (apart from the air peak) displayed on a common recorder, indicating a compound which was monitored, after having passed the column, in the mobile phase by the detector. The first parameter usually measured from the chromatogram is the retention time, tR, which represents the time period between the instant of sample injection at (I) (Fig. 1) or Start (Fig. 2) and the emergence of the peak maximum (Fig. 2) of a compound retained by the stationary phase. In addition to retention time, sometimes other terms are used for tR, e.g., total retention time of a solute and gross retention time. Unretained compounds, i.e., those not solved or adsorbed by the stationary phase, also need time to pass from (I) to (D). The same transit time through the column and the equipment is required by the mobile phase and it is therefore called the mobile time, tM. Other frequently used terms are gas hold-up time and air peak time (as air often represents an unretained substance).

Fig. 2 Gas chromatrogram showing the raw gas chromatographic data.

Obviously, the part of the retention time due to the residence of the retained compound in the stationary phase is

(1)

or, in other words, t’R represents that portion of time resulting from interactions of the molecules of this compound with the stationary phase, and is characteristic of this compound. Thus, t’R is the basis of almost all gas chromatographic calculations (except for the plate number). t’R is called the adjusted retention time. As other expressions occasionally applied to t’R, such as corrected retention time, net retention time and reduced retention time, could be misinterpreted and would confuse the gas chromatographer, only the terms

tR = retention time,

tM = mobile time, and

t’R = tR – tM = adjusted retention time

are used in this book.

These retention times either can be measured on the recording in units of length and converted into minutes and seconds or the times themselves can be determined directly if a data system is available. The mobile time, being an important value, can be timed in the same way, taking the air peak as the basis, if the stationary phase does not retain air (this generally applies to liquid phases above or near room temperature but not necessarily to solid stationary phases) and if an appropriate detector, e.g., a thermal conductivity detector, is used.

With a flame ionization detector methane is often used instead of air. One has to be aware, however, that the measured values are not correct at column temperatures below 50°C. Another possibility is to calculate the mobile time tM 4, 5.

Further raw data obtainable from the chromatogram are the peak height, i.e. the distance between the baseline and the maximum peak height, and the peak width at various proportions of the maximum peak height. Three characteristic widths should to be mentioned here (Fig. 2):

wI = peak width at the inflection points,

wH = peak width at half-height,

wB = peak width at the base (distance between the points of intersection on the baseline by the tangents to the curve through the inflection points).

2.3 Derived Basic Chromatographic Parameters

2.3.1 Retention Volume Terms

Retention Volume, VR

The volume of carrier gas flowing through the column during the retention time, tR, of a retained compound is

(2)

Fc[ml/min] = volumetric flow rate at the column temperature Tc [K] and the column outlet pressure p0 [MPa].

When measuring the flow rate (e.g. by means of a soap bubble flow meter, determination of the stream of carrier gas volume passing per time unit, stagnation dynamic pressure meter) we do not obtain Fc for the column temperature, but Fa at ambient temperature at the column outlet. Fa should therefore be corrected for at least the column temperature and, if water is present in the flow meter, for dry carrier gas conditions [5] to obtain Fc:

(3)

where

Tc = column temperature [K],

Ta = ambient temperature [K],