Table Of ContentOPEN TUBULAR
COLUMNS
IN GAS CHROMATOGRAPHY
OPEN TUBULAR
COLUMNS
IN GAS CHROMATOGRAPHY
L. S. Ettre
Chief Applications Chemist,
Analytical Division
The Perkin-Elmer Corporation, Norwalk, Connecticut
With a Foreword by
M. J. E. Golay
PLENUM PRESS
NEW YORK
1965
ISBN-13: 978-1-4684-0690-0 e-ISBN-13: 978-1-4684-0688-7
DOl: 10_1007/978-1-4684-0688-7
Library of Congress Catalog Card Number 65-13583
©1965 Plenum Press
Softcover reprint of the hardcover 1st edition 1965
A Division of Consultants Bureau Enterprises, Inc_
227 West 17th Street • New York, N. Y.10011
All rights reserved
No part of this publication may be reproduced in any
form without written permission from the publisher
To My Colleagues
at
Perkin-Elmer
Foreword
For my past sins, Leslie Ettre has given me the privilege of
writing a few words to preface his excellent little book. It gives me
great pleasure to do so, because of the many years of fruitful collabo
ration we have had at Perkin-Elmer, because it is refreshing to see
a treatise in gas chromatography in which the theoretical treatment
has been bared to its essentials, without a mushrooming of formulae
which, by means of an ever increasing number of parameters, account
for more and more, and explain less and less, and because the author
has recognized that the gas chromatographic column is a nearly
passive element in its own right which deserves to have a treatise
written nearly exclusively about it, just as electrical circuit theory
can be discussed without elaborate references to vacuum tubes and
meters.
I wish this conscientiously written volume the success it deserves.
M. J. E. GOLAY
VII
Preface
Gas chromatography is a separation technique used primarily
in analytical chemistry. Therefore, it is evident that special emphasis
should be placed on that particular part of the apparatus in which
the separation takes place. This part is the column, the heart of the
gas chromatograph.
The goal of researchers in the field of gas chromatography has
been-from the beginning-to understand the separation process so
that they might design columns with the best possible performance.
Such investigation led M. J. E. Golay in 1956~ 1957 to the develop
ment of a special column type. These columns are not filled with the
ordinary column material, which consists of a solid support and a
stationary (liquid) phase; rather the inside column wall itself serves
as the support and is coated with a thin film of the stationary phase.
As pointed out by W. W. Brandt [24], this invention "ranks as one
of the two or three major original developments in gas chromatog
raphy since its discovery by James and Martin."
In the years since Golay's invention, these columns have found
wide application in practically every field where gas chromatography
is used. The publications on the theory, instrumentation, and applica
tions of these columns are voluminous. However, with the exception
of Kaiser's excellent book [160], originally written in 1961, the
accumulated knowledge has not been summarized in one single
publication.
In November 1963, the author had the honor to present a lecture
at the Eastern Analytical Symposium in New York City, discussing in
detail some theoretical and practical aspects of open tubular columns
and their applications. In the following months, this lecture was
repeated by invitation-with the content continuously updated
on six different occasions, including the yearly Gas Chromatography
Institutes held at Canisius College, Buffalo, N.Y., and Fisk University,
Nashville, Tenn. In the discussions following these presentations, it
IX
x Preface
was often suggested that the text of the lecture be made available in
printed form. This is how the idea for this book was born: it is
based on these lectures, but the original text has been significantly
enlarged and modified; furthermore, chapters discussing questions
not included in the oral presentations were added in order to cover
the subject completely.
This book was written for the practical gas chromatographer: its
principal aim is to help him better understand this exceptional tool.
After a brief introduction, some theoretical aspects are discussed in
order to allow certain conclusions necessary in the actual application
of these columns to be drawn. This treatment was felt to be most
profi table since theory and practice cannot be separated. Subse
quently, questions concerning the preparation of the various column
types and special problems in connection with the gas chromato
graphic system in which these columns are used are discussed. Finally,
a complete bibliography of publications dealing with the theory and
applications of open tubular columns in gas chromatography, with
a short subject index, is given. Bracketed numbers in the text refer
to this bibliography, while other literature sources are given as
footnotes.
Most of the chromatograms shown in the figures were selected
to illustrate certain specific points discussed in the text rather than
to show the analysis of typical samples, primarily because it is the
author's experience from his long activity in gas chromatography
that no "typical sample" exists. Also, the principal purpose of the
chromatograms is to illustrate some practical applications, to draw
attention to the most important fields to which open tubular columns
can be successfully applied, and not to reproduce the best chromato
grams ever published. It was felt that the basic goal of the book is
not to give a collection of chromatograms but to help in better
understanding the characteristics of open tubular columns.
The various units of measurement used by different authors in
describing the columns and analytical conditions represented a serious
problem. Although in this book the metric system is used whenever
possible, data on column length and inlet pressure were left as given
originally by the authors because the transformation of feet and
pounds per square inch into the corresponding metric units would
often result in irrational numbers. However, the internal diameter
of the column is always given in metric units, in order to make
comparison and calculation simpler.
Preface XI
Since this book discusses the open tubular columns, the instru
mentation used to obtain the various chromatograms is not mentioned
in the figure captions; however, it is summarized in the Supplement.
Great care was taken to establish a logical nomenclature. The
symbols used are based on the recommendations of the various
international symposia and the special I.U.P.A.C. Committee;
symbols corresponding to terms not included in their treatment were
established by selecting the most logical usage. In this respect, our
goal was to have only one meaning for each symbol.
This book is based on both the literature and the experiences
collected in the last eight years at the various laboratories of The
Perkin-Elmer Corporation, where the original work of Dr. Golay
was carried out. The author wishes to express his sincere appreciation
to all colleagues and sources listed in the following pages who placed
at his disposal various published and unpublished material. Special
thanks are due to W. Averill, N. Brenner, R. D. Condon, and S. D.
Norem at Perkin-Elmer and Dr. C. Horvath at the Research Labor
atory of the Massachusetts General Hospital, Boston, who read
parts of the manuscript and were instrumental, by their thoughtful
advice and criticism, in molding its final shape; further, to the manage
ment of The Perkin-Elmer Corporation, Norwalk, Conn., for per
mission to write this book and for allowing the use of various com
pany facilities. The fine cooperation of J. R. Piccolo and E. Hagen
burger in the preparation of the illustrations and of Mrs. E. Barrett
in typing the manuscript is particularly noteworthy. Last but not
least, the efforts of Plenum Press in making possible the publication
of this book in an unusually short time are greaty appreciated.
It is the author's sincere hope that this work will give the practi
cal gas chromatographer a better understanding of the characteristics
of open tubular columns and help him in improving his everyday work.
Norwalk, Connecticut L. S. ETTRE
August 20, 1964
Acknowledgments
The illustrations in this book, aside from those constructed by
the author, come from a variety of sources. Reproduction of the
following illustrations is authorized through the courtesy of the
publications, corporations, and persons named:
Analytical Chimica Acta (Elsevier Publishing Co., Amsterdam, The Netherlands):
Figure 30.
Analytical Chemistry (American Chemical Society, Washington, D.C., USA): Figures
27, 38, 50, 51.
Brennst()tf~Chemie (Girardet Verlag, Essen, Germany): Figures 24, 25.
Chemistry & Industry (Society of Chemical Industry, London, England): Figure 31.
Instrument News (The Perkin-Elmer Corp., Norwalk, Conn., USA): Figures 16, 17.
Journal of Chromatography (Elsevier Publishing Cn .. Amsterdam. The Netherlands):
Figures 28, 61, 74, 75.
Journal of Gas Chromatography (Preston Technical Abstracts Co., Evanston, Ill.,
USA): Figures 5, 7, 34, 37, 42, 43, 44, 48, 49, 54, 73.
Nature (Macmillan (Journals) Ltd., London, England): Figures 56, 57, 58, 69.
Barber-Colman Co., Rockford, IlL, USA: Figure 32.
Bodcnseewerk Perkin-Elmer & Co., Uberlingen, Germany: Figures 18, 26, 29, 36,
45,47, 65, 67, 76.
Butterworths Inc., Washington, D.C., USA: Figure 53.
Perkin-Elmer Corp., Norwalk, Conn., USA: Figures 6, 19, 20, 21, 35, 46, 55, 59, 64,
66, 68, 70, 71, 72.
W. Averill (Perkin-Elmer Corp., Norwalk, Conn., USA): Figure 41.
E. W. Cieplinski (Perkin-Elmer Corp., Norwalk, Conn., USA): Figure 66.
C. Horv,lth (Massachusetts General Hospital, Boston, Mass., USA): Figure 52.
F. 1. Kabot (Perkin-Elmer Corp., Norwalk, Conn., USA): Figures 14, 33.
1. Ocsterhelt (Bodenseewerk Perkin-Elmer & Co., Uberlingen, Germany): Figure 45.
XIII
Symbols
a Constant in Eq. (50)
aK Constant in Eq. (51)
a Accommodation coefficient in gas-solid adsorption chromatography
A Peak area
b Constant in Eq. (50)
B Longitudinal gaseous diffusion term
Bo Specific permeability
c Concentration of the coating solution
Minimum detectable concentration in a given sample
Term of resistance to mass transfer in the gas phase
Mass transfer term for the kinetics of adsorption and desorption In
gas-solid adsorption chromatography
C Term of resistance to mass transfer in the liquid phase
L
d Inside diameter of column tubing
df Average thickness of the liquid-phase film
d Effective particle diameter of the support
p
d Density of the liquid phase
L
DG Gaseous diffusion coefficient
DL Liquid diffusion coefficient
f A square root function of k [see Eq. (29)]
Fl, F2 Factors used in chapter 2.322
F A verage carrier gas flow rate
F. Carrier gas flow rate measured at column outlet and ambient tempera-
ture
Fe Value of F. corrected to column temperature
HETP Height equivalent to one theoretical plate
HETP The theoretical minimum value of the HETP curve
min
j Carrier gas compressibility correction factor
k Partition (capacity) ratio
K Partition coefficient
L Column length
m Constant in Eq. (64)
M Amount of coating in the column
n Number of theoretical plates
Number of carbon atoms in a molecule
Number of theoretical plates calculated from Eq. (47)
Number of theoretical plates required in order to achieve a desired
resolution for a given component pair
N Number of effective plates
xv
