trends in analytical chemistry, vol. 21, nos.
9+10, 2002
History of gas chromatography+
Keith D. Bartle*, Peter Myers
School of Chemistry, University of Leeds, Leeds LS2 9JT, UK
Modern gas chromatography (GC) was invented by
Martin and James in 1952 [1], and has become one
of the most important and widely applied analytical
techniques in modern chemistry. Major milestones in
the development of GC, especially in column tech-
nology, detection and sample introduction are
described in this historical review. Many trends in
current progress can be seen to originate in the first
two decades of the history of GC, but the invention
of fused-silica capillary columns greatly increased the
application of high-resolution GC across the field of
organic analysis; the development of low-cost,
bench-top mass spectrometers led to further advan-
ces. Progress continues to be rapid in comprehensive
2D GC, fast analysis, detection by atomic emission
and time-of-flight mass spectrometry, and in appli-
cations to process analysis. # 2002 Published by
Elsevier Science B.V. All rights reserved.
1. What is gas chromatography?
Our world is one of complex mixtures. Pet-
roleum may well contain over 100,000 compo-
nents. It is thought that there are of the order of
100,000 different proteins in the human body.
And natural products, such as essential oils, are
also often highly complex. Separation methods
are necessary to analyse these, while even the
simpler, but still often difficult, mixtures
encountered in, for example, the pharmaceutical
industry most often require chromatography or
a related technique.
Separations are achieved by GC by a series of
partitions between a moving gas phase and a
+
Based, in part, on a lecture in November 2001 at the desig-
nation by the Royal Society of Chemistry of a National Histor-
ical Landmark on the Leeds, UK, site of the invention of
partition chromatography by A.J.P. Martin and R.L.M. Synge.
*Corresponding author. Tel.: +44 (0)113 2336490; Fax: +44
(0)113 2336565. E-mail: k.d.bartle@chem.leeds.ac.uk
0165-9936/02/$ - see front matter
PII: S0165-9936(02)00806-3
547
stationary liquid phase held in a small diameter
tube (the column) after a mixture is injected as a
narrow band. A detector then monitors the
composition of the gas stream as it emerges
from the column carrying separated compo-
nents, and the resulting signals provide the input
for data acquisition. GC can be applied to the
analysis of mixtures, which contain compounds
with boiling points from near zero to over 700
K, or which can be heated sufficiently without
decomposition to give a vapour pressure of a
few mmHg. Derivatisation to increase volatility
extends this range. The sample size can be as
small as pg, but, in preparative, as opposed to
analytical, applications, tens of grammes can be
handled.
GC is now a standard analytical method that
underpins research, development, and quality
control in many industries, especially petro-
chemical manufacture, and in environmental,
food contaminant, and drug residue and foren-
sic analysis.
2. Origin of GC
The invention of GC is generally attributed to
A.T. James and A.J.P. Martin in their 1952
paper [1] which followed a presentation on 20
October 1950 at a meeting of the Biochemical
Society, with wide interest generated by a lecture
at a Society of Chemical Industry meeting in
Oxford in September 1952. They reported the
separation of volatile fatty acids by partition
chromatography with nitrogen gas as the mobile
phase and a stationary phase of silicone oil/
stearic acid supported on diatomaceous earth.
In fact, the origin of GC lies in a sentence,
overlooked by other researchers, in the 1941
publication [2] in which Martin, with R.L.M.
Synge, first described liquid-phase partition
# 2002 Published by Elsevier Science B.V. All rights reserved.
548
chromatography: ‘‘Very refined separations of
volatile substances should be possible in a col-
umn in which permanent gas is made to flow
over gel impregnated with a non-volatile
solvent. . .’’.
The novel aspect of Martin’s work was the
employment of partition as the separation prin-
ciple, although gas adsorption chromatography
was also developed in the 1940s and 1950s by a
number of researchers (notably Hesse, Cramer,
and Phillips [3]).
James and Martin followed their first paper
with reports in the same year of the analysis of
bases by GC [4,5]. A photograph of Martin
demonstrating GC on a version of his first GC
is shown in Fig. 1.
One of the greatest analytical challenges of the
1950s was the composition of petroleum, then
replacing coal as the predominant source of
liquid fuels and chemical feedstocks. The
petroleum industry rapidly adopted GC for
compositional analysis, with outstanding
developments and applications, with researchers
at Shell (e.g. Keulemans and Adlard) and British
Petroleum (Desty) at the forefront [3].
GC also enjoyed explosively rapid growth in
the decade after its discovery in a host of other
application areas [6], especially biochemistry [7],
including amino-acid analysis [8], and natural
product (e.g. steroids [9]), and food and flavour
[10] studies. Another driving force in putting
GC on a firm physico-chemical basis (see, for
Fig. 1. Video photograph of Martin and James’s GC.
trends in analytical chemistry, vol. 21, nos. 9+10, 2002
example, the monograph by Purnell published
in 1962 [11]) was its application in the investi-
gation of reaction kinetics [12]. As many as 200
papers on the analysis of fatty acids and fatty
acid esters had appeared by 1960 [6]. Rapid
expansion continued, with an exponential
growth of capillary column GC (see below) in
the 1980s.
3. The gas chromatograph
The early pioneers of GC would have no dif-
ficulty in recognising the layout of a modern
instrument, shown schematically in Fig. 2. The
main item is the column, originally a tube
packed with a solid support coated with the
stationary liquid, but now a fine tube with the
liquid coated on the inner surface. The carrier
gas, at first nitrogen, but now helium or hydro-
gen, passes from a cylinder through a pressure-
or flow-rate-controlling device to the sample
injector at the column inlet. When the separated
mixture components of the mixture emerge
(‘‘are eluted’’) from the column, they are detec-
ted by the measurement of some chemical or
physical property. An important factor influen-
cing column performance is its temperature; for
most mixtures, it is necessary to work at higher
temperatures, and good temperature control is
always important, originally achieved by enclos-
ing the column in a vapour jacket or thermo-
statted block, but now in a hot-air oven.
Resistive heating of metal-clad columns to allow
extremely rapid heating and cooling is also being
introduced.
3.1. Columns for GC
The column is at the centre of the analytical
gas chromatograph; the quality of the separation
achieved by the whole system can be that of the
column only. Early GC was carried out on
packed columns, typically 1–5 m long and 1–5
mm i.d., and filled with particles each of which
was coated with a liquid or elastomeric sta-
tionary phase. Micro-packed columns are simi-
lar but have i.d. <1 mm. The resolution of
trends in analytical chemistry, vol. 21, nos. 9+10, 2002
Fig. 2. Schematic diagram of a basic gas chromatograph. (Reproduced with permission of John Wiley and Sons Limited).
packed columns is limited by their length, itself
restricted by the pressure drop consequent on
the resistance to gas flow. This restriction was
removed by the invention of the capillary col-
umn, suggested by Martin [13] at a meeting in
1956, but independently realised in 1957 by
Golay [14], who laid out the theory of operation
and demonstrated its use in 1958 [15].
In a capillary column, the stationary phase is
coated on the inner wall, either as a thin film
(wall-coated open tubular) or impregnated into
a porous layer on the inner (porous layer or
support coated open tubular), and the differing
paths taken by solute molecules as they pass
through the (inevitably) non-uniform packing
(i.e. a bundle of capillaries) is replaced by a sin-
gle channel. As well as the advantage over
packed columns of greatly increased separation
efficiency, capillary columns work at a lower
temperature, and give much better separation
(see Fig. 3) in equal times, or the same separa-
tion in shorter time (Table 1). Results are gen-
erally generated up to 10 times faster than in a
Table 1
Comparison of wall-coated capillary, support-coated open tubular, and packed columns
Wall-coated capillary
Length (m) 10–100
Internal diameter (mm) 0.1–0.8
Liquid film thickness (mm) 0.1–1
Capacity per peak (ng) < 100
Resolution High
549
packed column. Of course, the much smaller
amounts of stationary phase in a capillary col-
umn mean that their capacity is limited, and
special sample-introduction methods (see Sec-
tion 3.5) and sensitive detectors (see Section 3.3)
are required.
A number of column materials were
employed in the early history of capillary GC —
copper, nickel, stainless steel, and even nylon
tubing — but the relative inertness and trans-
parency of glass columns were quickly recog-
nised as advantageous. In 1961, Desty [16]
proposed a device that drew out and coiled
glass capillary tubing from laboratory glass tube.
Glass capillary columns were widely used until
1980, with a voluminous literature devoted to
their preparation (see e.g. [17–19]) with land-
mark contributions from the groups of
Novotny, Grob Sr., and Schomburg. Progress
with glass columns was impeded, however, by
their fragility, and activity towards highly polar
analytes. These problems were to a large extent
solved by the invention of fused-silica columns
Support-coated open tubular Packed
10–50 1–5
0.5–0.8 2–4
0.8–2 10
50–300 10,000
Moderate Low
550
Fig. 3. Chromatograms of Calmus oil on (A) a 50 m capillary column and (B) a 4 m packed column with the same stationary
phase.
in 1979 by Dandeneau and Zerenner [20]. Such
columns, manufactured by a process originally
based on fibre-optic technology, are highly flex-
ible, durable and chemically inert. Externally
coated with a protective layer of polyimide and
with an immobilized film of one of a wide
variety of stationary phases, fused-silica col-
umns provide the means of separation of
almost all mixtures to be analysed; the few
exceptions, such as permanent gases and low
molecular-weight compounds, are separated on
porous layer open-tubular columns with, for
example, alumina-based stationary phases [21].
Extensive research was carried out in the
1980s, notably by the group of Lee [22–24], to
determine the physical chemistry principles
underlying coating of fused-silica columns with
a uniform, homogeneous and stable film of
stationary phase. While the fused-silica surface
trends in analytical chemistry, vol. 21, nos. 9+10, 2002
is substantially free of the metallic oxides that
act as Lewis-acid adsorption sites for polar and
aromatic molecules on glass columns, it still has
a number of reactive hydroxyl groups attached
to the surface silica atoms; these active sites
must be deactivated by high-temperature silyla-
tion. Clean fused-silica is a high-energy surface
and is hence wettable by most organic liquids.
But, after the deactivation step, only stationary
phases of appropriate surface tension will
spread, since the critical surface tension of the
surface is greatly reduced, although it can be
adjusted by the presence of the necessary func-
tional group in the deactivating reagent. The
wettability of a column surface is not influenced
by high temperature, since changes in the sur-
face tension of the phase are matched by chan-
ges in the critical surface tension of the surface.
However, the stationary phase film is still
trends in analytical chemistry, vol. 21, nos. 9+10, 2002
inherently unstable [25] — so-called Rayleigh
instability. The rate of rearrangement of the film
depends inversely on its viscosity, and disrup-
tion and stationary phase ‘bleed’ is overcome by
in-situ cross-linking of (usually) unsaturated
groups in the stationary phase molecule by
means of free-radical initiators, such as per-
oxides, or best, azo compounds to yield elasto-
mers.
Column manufacturers now make available a
wide range of capillary columns, making use of
the principles discussed above. The choice of
the appropriate column for a given required
separation depends on the chemical nature of
the analyte, the sample matrix, and the solvent
(for a summary, see [26]), and especially on the
nature of the molecular interactions between
analyte and stationary phase. Dispersive (non-
polar) interactions give rise to separations based
on analyte volatility, of which a simple measure
is boiling temperature, while dipole-dipole
interactions, and hence increased retention and
selectivity, occur between solutes and stationary
phases with polar groups (e.g. cyanopropyl and
trifluoropropyl). A polar stationary phase or
analyte may also induce a dipole moment in an
electron-rich solute or phase and hence result in
selective interactions. Analytes capable of
hydrogen bonding may be separated by a sta-
tionary phase containing hydroxyl groups, such
as polyethylene glycol. Shape-selective separations
are also possible with chiral or liquid-crystal
stationary phases.
The first stationary phases for GC were a
varied collection of hydrocarbon and silicone
oils and greases, esters and polymers, but now
by far the largest number of GC stationary
phases are based on a cross-linked polysiloxane
backbone with appropriate pendant groups (e.g.
CH3, Ph, CH2–CH2–CH2–CN, CF3) The pen-
dant group may also be tailored for a steric
separation. A number of so-called ‘wax’ poly-
ethylene glycol phases are also popular. A sily-
larene backbone increases the temperature
stability of the phase.
Other choices in capillary column selection
include column internal diameter (dc), film
thickness (df) and length (L). It follows from
551
Golay’s 1958 theoretical treatment [15] that the
number of theoretical plates, N, is proportional
to 1/d2c ; the narrower the column, the greater
the resolution, but the less the capacity. Values
of dc of 100–500 mm are standard, with df 0.25–
0.5 mm. Column lengths vary from 5 m to
> 100 m, but the advantages of increased effi-
ciency in long columns are offset by increased
analysis times and the fact that resolution
depends on N1/2 and hence L1/2; quadrupling L
only doubles resolution. There is an increasing
trend to shorter, narrower columns.
Elution of analytes is brought about by hold-
ing the temperature of the column at a high
enough value to ensure solubility in the gas
phase, a process well characterised by 1962 [11].
However, for mixtures with a wide range of
volatilities, the spreading of late-eluting com-
pounds can be overcome by programmed tem-
perature GC (PTGC) i.e. increasing the column
temperature during the run, a procedure inven-
ted by Griffiths et al. as early as 1952 [27]; pro-
gress and increase in use of PTGC were so
rapid that it was already the subject of a book
published in 1966 [28] and has been the pre-
dominant technique for many years.
3.2. Pneumatic systems in GC
With the advent of capillary columns, greater
precision was required in the pneumatic control
systems. Control of the gases required to run a
GC has been through a combination of on-off
valves, forward and back-pressure regulators,
needle valves and mass-flow-control regulators.
These have evolved together with the instru-
mentation, such that today we see total feedback
controls to maintain constant flow rates of the
carrier gases by monitoring the gas pressures
and flow rates that, in turn, control electronic
regulators. Much of the flow regime in capillary
instrumentation is closely associated with the
requirements of sample injection and this is now
possible through the automatic computer con-
trol of the pneumatics. As the instruments have
evolved, we have seen a trend towards the use
of keypads, either on the instrument or on a
separate keypad, to set the conditions of the
552
instrument. With the advent of the modern PC,
control tended to move to control and data-
acquisition programs on the PC. Now, it is
possible with the automatic flow-control mod-
ules to function under mass control or pressure
control of the carrier gas. This allows a choice
of constant pressure, constant flow or even
pressure programming.
3.3. Detection in GC
The first gas chromatograms were generated
by an automated titration system. But, in 1954,
Ray used the temperature (and hence electrical
resistance) change of a filament of a thermal
conductivity-measuring device — a katha-
rometer — as a means of detection [29]. The
katharometer remained popular for packed-col-
umn work because of its response to most ana-
lytes, but the requirement of trace analysis and
the development of the capillary column quickly
resulted in a new emphasis. Rather than use
bulk properties (based e.g. on gas density, flow-
impedance, and gravimetry - a sensitive version
of the latter was proposed by Martin [30] in
1962 as potentially the ‘‘ideal detector for GC’’),
more sensitive ionization-based detectors were
investigated.
While a number of flame-based detectors
based on flame temperature and emissivity had
already been devised, in 1958, Harley et al. [31]
and McWilliam and Dewar [32] realized, almost
simultaneously, that the thermal energy of a
hydrogen/air flame should bring about emission
of electrons from organic molecules in the
flame to produce ions, so that the measured ion
current would depend on the amount of eluent
per unit time entering the flame. The flame
ionisation detector (FID) was more sensitive
than the katharometer by a factor of 103–104,
with sub-ng detection limits demonstrated [32].
The FID rapidly became, and has remained,
extremely popular, overtaking a number of
other ionisation detectors proposed at the same
time [33]. Its low cost, unsurpassed linearity,
linear dynamic range and sensitivity for carbon-
containing compounds (Table 2) still make it the
universal detector of choice, although the mass
trends in analytical chemistry, vol. 21, nos. 9+10, 2002
spectrometer (see below) is having an increasing
impact, and the helium ionisation detector is a
modern ionisation detector with a better
response to a number of compounds, for which
the FID has limitations.
A number of ionization detectors other than
the FID originated at about the same time, for
selective detection. The electron-capture detec-
tor (ECD) of Lovelock and Lipsky [34], based
on the ability of a molecule to capture free
electrons from a b radiation source, has since
found wide acceptance as an extremely sensitive
detector (pg to fg range) for halogen-containing
compounds, with wide applications to trace
pesticide residues. The analysis of atmospheric
chlorofluorocarbons, destroyers of the strato-
spheric ozone layer, represents a particular
triumph for the ECD. Among a number of non-
radioactive ionization detectors, the photo-ioni-
zation detector (PID), again due to Lovelock
[35], and the alkali flame or thermionic detector
(TID) have also found long-standing applica-
tion. Depending on the discharge gas, which
determines photon energy, and the materials of
the optical window, the PID allows selective
detection for e.g. aromatics over aliphatic com-
pounds. In the TID, selective detection, parti-
cularly for nitrogen and phosphorus
compounds (thus making the detector particu-
larly useful in trace herbicide and pesticide ana-
lysis), is achieved by an alkali-metal salt placed
near a hydrogen/air flame. The original TID,
invented in 1964 by Kamen and Giuffrida [36],
employed a volatile alkali salt attached to the
FID flame jet, but new versions [37] used an
externally heated alkali source, such as a rubi-
dium silicate bead.
Non-ionization flame detectors proposed in
early GC included the flame emissivity detector,
suggested by Grant in 1956 [38], which had
high selectivity for aromatics. But the most
commonly used flame emission detector is the
flame photometric detector (FPD), in which
light-emitting combustion products are gener-
ated, especially of sulphur compounds, in a cool
hydrogen-rich flame. The dual-flame version of
the FPD has advantages over the original 1966
single-flame FPD of Brody and Chaney [39].
trends in analytical chemistry, vol. 21, nos. 9+10, 2002
The ultimate element-selective detector for
GC (Table 2) is the atomic emission detector
(AED). As early as 1965, McCormack used [41]
a microwave-induced plasma (MIP) in GC
detection, and a variety of other emission sour-
ces, both flame and plasma, have been investi-
gated [42]. An important advance came in 1990
when Quimby and Sullivan [43] developed an
AED with a water-cooled MIP with a number
of reagent gases to enhance performance for
elements hitherto exhibiting poor sensitivity,
such as N and O. The spectrometer incorpo-
rates a photodiode array with a wavelength
range of 160–800 nm so that elements across
the periodic table can be detected - up to four
simultaneously. The high sensitivity and selec-
tivity, linearity and compound-independent
response have led to numerous applications, to
not only the more usual S, N, P, halogens, etc.,
in a wide variety of analytes, but also Sn (in
fungicides), V and Ni (petroleum porphyrins),
and Hg and Pb compounds. The on-line use of
AED, combined with mass-spectrometric
detection for tracing targets as well as
unknowns, was another powerful addition [44].
3.4. Mass spectrometric detection
It was realised early that the structural infor-
mation and selectivity available from mass
spectrometry (MS) made the combination of
MS with GC the most effective technique for
the analysis of complex mixtures. While off-line
analyses of GC fractions were made initially,
Gohlke described in 1959 [45] the direct intro-
duction of GC effluent into a mass spectro-
Table 2
Properties of commonly used detectors on capillary GC [40]
FID ECD
Operation mode Mass flow rate Concentration
Selectivity Organic carbon Electron affinity
Detection limit 0.5 pg/s 1pg/mL
Linearity 107 104
Destructive Yes No
553
meter, and detailed GC-MS analysis of natural
products was being reported by 1963. The high
cost of MS instrumentation and the incompat-
ibility of high GC flow rates in packed columns
with the vacuum requirements of the mass
spectrometer both hindered progress of GC-
MS. However, the much smaller flow rates in
capillary columns, along with the enrichment
possible with molecular separators made GC-
MS more attractive. GC-MS was advanced
enough in the 1970s for an instrument to form
part of the Viking Mars Lander [46]. The avail-
ability of less expensive bench-top MS led to the
routine use of the GC-MS technique in the
1980s and it is now pre-eminent. Time-of-flight
MS was endorsed by Martin in 1962 [30]
because of its inherent sensitivity, but only
recently has its performance been developed to
allow routine coupling to GC.
In GC-MS of all types, as in other GC ioni-
sation detectors, ions are produced by electron
or chemical ionisation but are now sorted
according to molecular weight (or mass-to-
charge, m/z, ratio) by one of a range of analy-
sers: magnetic sector; (less expensive) quadru-
pole or ion-trap in ‘bench-top’ instruments; or
time-of-flight. The resulting mass spectrum is
related to the molecular weight and structure of
the analyte, and allows identification through
comparison with a library, or through a-priori
interpretation. The MS detector can be operated
in either scanning mode or, in a technique
introduced in 1968 [47], with selected-ion mon-
itoring. Thus, a range of m/z values may be
scanned (say 50–500) in a bench-top instrument
in 1 s, typically. A computer is then used to plot
PID TID FPD
Concentration Mass flow rate Mass flow rate
Hydrocarbons (aromatics) N/P S/P
0.5 pg/mL 25 fg/s (P) 50 fg/s (N)
50 pg/s (S) 0.5 pg/s (P)
107 104(P) 103(S)
105(N) 105(P)
No Yes Yes
554
either the total-ion current (analogous to the
response of a universal TC detector) or indivi-
dual ion currents (‘‘mass chromatograms’’),
which may be specific to selected compound
types; much greater sensitivity is achieved by
monitoring only one ion or a few ions.
The great advantages of time-of-flight MS lie
in the possibilities for accurate mass measure-
ment (in contrast to the unit m/z resolution of
‘‘bench-top’’ MS), which allow the molecular
formulae of ions to be determined, and rapid
rates of accumulation of spectra (up to 500 Hz),
which allow GC peaks with widths as narrow as
12 ms to be identified [48].
3.5. Sample introduction in GC
Injection of a sample into the gas stream at
the column head was already carried out in early
work by means of a syringe and a hypodermic
needle. At first, a re-sealable rubber ‘‘subaseal’’
cap was employed, but this was replaced as early
as 1964 by a heat-resistant elastomeric septum
compressed in a metal fitting, the procedure
which has persisted until now. Because injection
of a representative part of the sample as a
narrow band in a quantity consistent with the
capacity of the capillary column is often a limit-
ing factor, a variety of injection methods have
been developed. The basic splitter injector,
which allows a small fraction of a rapidly vola-
tilised sample to enter the column while the
major portion is vented to waste, was intro-
duced by Desty in 1959 [49] and much devel-
opment of this device followed [50].
The injection of 20–100 mL liquid volumes is
now routinely possible, rather than the formerly
standard 1–2 mL, by using sample-introduction
systems, such as on-column, loop-type, and
programmed temperature vaporization (PTV)
[51]. A 100 mL injection will easily allow
measurement of solute concentrations of 100
ppt. The conventional splitting injection may be
used to allow large volumes of a dilute sample
solution to be introduced into the column at
low temperature by simply closing the split
valve. Grob and Grob [52] showed that the
more volatile excess sample passes through, and
trends in analytical chemistry, vol. 21, nos. 9+10, 2002
trace solutes are concentrated in a narrow band
in the column — a technique routinely used in
environmental analysis, analysis of pesticides in
foods, and drug screening.
The possibility of sample loss during vapor-
isation of a liquid sample and transfer of vapour
to the column can be eliminated by direct
injection into the inlet of the column. The use
of a syringe for on-column injection into a wide-
bore capillary was first described by Zlatkis in
1963 [53] and later adapted and developed by
the Grobs [54] for smaller diameter columns
into a technique widely used today. Other more
specialised sample-introduction systems became
available for capillary GC and include the PTV
injector, and a variety of pyrolyzer systems [22].
PTV injectors can be used in split, splitless or
direct mode. Here, the inlet temperature is
maintained below the boiling points of solvent
and solutes, but is rapidly programmed to
vaporize each component in turn. Solutes are
then exposed to less thermal stress and large
volumes can also be injected.
Low levels of volatile organics in environ-
mental matrices may be analysed by headspace,
dynamic stripping or purge-and-trap sampling.
In purge-and-trap, the sample is purged with
helium and volatile analytes collected on a trap
of adsorbent material from which they are
released by rapid heating.
4. Multi-dimensional GC
Two-dimensional (2D) chromatography was
suggested by Martin in 1944 [55]. A consider-
able increase in peak capacity is achieved if a
mixture to be analysed is subjected to two cou-
pled separations with different separation
mechanisms [56]. On-line coupling of liquid
chromatography (LC) with capillary GC was
reported [57] by Majors in 1980, and Grob used
concepts developed in his laboratory for large-
volume GC injection to achieve considerable
improvements in coupled LC-GC [58].
In 1968, Deans showed [59] heart-cutting via
the so-called ‘‘Deans switch’’ fluidic valve of a
region of a GC chromatogram into a second
trends in analytical chemistry, vol. 21, nos. 9+10, 2002
Fig. 4. Photograph of the Stanford GC-on-a-Chip.
column with different polarity, and Schomburg
demonstrated [60] how this could be achieved
for capillary columns. Fully comprehensive GC-
Fig. 5. Photograph of a modern portable GC (Reproduced
with permission from Varian).
555
GC (so-called GCxGC) should, in principle,
achieve the maximum degree of component
separation, and this was first carried out in 1991
by Phillips [61] by modulated injection of con-
secutive short-time period fractions from a
conventional capillary GC column for rapid
analysis in a much shorter second column.
Remarkable separations of, especially fossil fuels
[56], essential oils and air pollutants [62] have
been observed.
5. Conclusion and future of GC
GC expanded with great rapidity over the two
decades following its invention in 1952, and
much current practice has its roots in that
period. The introduction of robust, efficient and
reproducible fused-silica capillary columns and
the provision of relatively inexpensive but reli-
able equipment for GC-MS provided a crucial
new impetus in the 1980s. High-speed GC, time-
of-flight MS, AED, and comprehensive GCGC
now promise further expansion. The versatility of
modern GC will expand its application areas.
In particular, chromatography has a vital role to
play in process control in chemical industry, and
on-line and at-line GC methods are replacing
analysis in a central laboratory, continuing a trend
begun at Shell refineries in 1956 [63]. Fast-GC
separations, first demonstrated by Desty in 1962
Fig. 6. Dr. Lipsky (right) and Maurice Godet, working on a
1950s GC. Not a small device. (Reproduced with permis-
sion from the Quadrex Corporation).
556
[64] using miniaturised instruments for process
[65] and field-monitoring [66] applications (a GC
system for airborne atmospheric monitoring now
flies routinely!), are now available.
The first known reference to a GC-on-a-chip
was made verbally by James Lovelock in the
early 1970s. It was made on a magnesium oxide
chip, less than 50 mm20 mm. It used elec-
trolytic and coulometric methods to produce
the gas. The Stanford GC was also reported in
the 1970s. Shown in Fig. 4, it was a complete,
working GC on a silicon wafer, including
column, injector and detector. A number of
attempts were made to commercialize this, but
all failed. It is only relatively recently that reliable
microfabricated components have started to
appear in GCs, but we still await a truly hand-
held, portable, small unit. Today, the closest is
the Varian Micro GC. It contains its own carrier
gas and power supply in a unit measuring only
15 cm25 cm36 cm and weighing only 7 kg
(Fig. 5). It makes an interesting comparison with
a GC from the late 1950s (Fig. 6).
GC has not only 50 years of history, but an
exciting future.
Acknowledgements
The authors are grateful to a number of
chromatographers for helpful discussions dur-
ing the preparation of this article, especially Ted
Adlard, David Grant, Ally Lewis and Luigi Mon-
dello. The views expressed, however, are our own;
history can only be subjective, and we apologise
both for inevitable omissions and for conflicts
between our recollections and those of others!
References
[1] A.T. James, A.J.P. Martin, Biochem. J. 50 (1952) 679.
[2] A.J.P. Martin, R.L.M. Synge, Biochem. J. 35 (1941) 1358.
[3] E. Smolková-Keulemansová, J. High Resol. Chromatogr.
23 (2000) 497.
[4] A.T. James, A.J.P. Martin, G.M. Smith, Biochem. J. 52
(1952) 238.
[5] A.T. James, Biochem. J. 52 (1952) 242.
[6] S. Dal Nogare, R.S. Juvet Jr., Gas-Liquid Chromato-
graphy, Interscience, New York, USA, 1962.
trends in analytical chemistry, vol. 21, nos. 9+10, 2002
[7] S.R. Lipsky, R.A. Landowne, Ann. Rev. Biochem. 29
(1960) 649.
[8] A. Zlatkis, J.F. Oro, A.P. Kimball, Anal. Chem. 32 (1960)
162.
[9] G.R., Eglinton, R.J., Hamilton, R., Hodges, R.A., Raphael,
Chem. Ind. (London) (1959) 955.
[10] W.G. Jennings, S. Leonard, R.M. Pangborn, Food Tech-
nol. 14 (1960) 583.
[11] H.G. Purnell, Gas Chromatography, John Wiley, New
York, USA, 1962.
[12] J.H. Knox, , Chem. Ind. (London) (1955) 1631.
[13] A.J.P. Martin, D.H. Desty (Editors), Vapour Phase Chro-
matography, Butterworths, London, 1957, p. 2.
[14] M.J.E. Golay, in: V.J. Coates (Editor), Gas Chromato-
graphy (1957) (Lansing Symposium), Academic Press,
New York, USA, 1958, p. 1.
[15] M.J.E. Golay, in: D.H. Desty (Editor), Gas Chromato-
graphy, Butterworths, London, 1958, p. 36.
[16] D.H. Desty, J.N. Haresnape, B.H.F. Whyman, Anal.
Chem. 32 (1960) 302.
[17] M. Novotny, K.D. Bartle, Chromatographia 7 (1974) 122.
[18] K. Grob, Chromatographia 8 (1975) 423.
[19] G. Schomburg, H. Husmann, F. Weeke, J. Chromatogr.
99 (1974) 63.
[20] R.D. Dandeneau, E.H. Zerenner, J. High Res. Chroma-
togr. 2 (1979) 351.
[21] L.S. Ettre, J.E. Purcell, Adv. Chromatogr. 10 (1974) 1.
[22] M.L. Lee, F.J. Yang, K.D. Bartle, Open Tubular Column
Gas Chromatography, Wiley, New York, USA, 1984.
[23] C.L. Woolley, K.E. Markides, M.L. Lee, K.D. Bartle, J.
High Res. Chromatogr. 9 (1986) 506.
[24] B.W. Wright, B.E. Richter, M. Lee, in: M. Novotny (Edi-
tor), Recent Advances in Capillary Chromatography,
Wiley, New York, USA, 1982.
[25] K.D. Bartle, C.L. Woolley, K.E. Markides, M.L. Lee,
R.S. Hansen, J. High Res. Chromatogr. 10 (1987) 128.
[26] W. Jennings, E. Mittlefehldt, P. Stremple, Analytical Gas
Chromatography, 2nd Edition, Academic Press, New
York, USA, 1997.
[27] J.H. Griffiths, D.H. James, C.S.G. Phillips, Analyst 77
(1952) 897.
[28] W.E. Harris, H.W. Habgood, Programmed Temperature
Gas Chromatography, Wiley, New York, USA, 1966.
[29] N. Ray, J. Appl. Chem. 4 (1954) 21.
[30] A.J.P. Martin, in: M. van Swaay (Editor), Proceedings 4th
International Symposium on GC, Hamburg, 1962, Butter-
worths, London, 1962, p. xxvii.
[31] J. Harley, W. Nel, V. Pretorius, Nature 181 (1958) 177.
[32] I.G. McWilliam, R.A. Dewar, Nature 181 (1958) 760.
[33] B.J. Gudzinski, in: L.S. Ettre, A. Zlatkis (Editors), The
Practice of Gas Chromatography, Interscience, New York,
USA, 1967, p. 239.
[34] J.E. Lovelock, S.R. Lipsky, J. Amer. Chem. Soc. 82 (1960)
431.
[35] J.E. Lovelock, Anal. Chem. 33 (1961) 162.
[36] A. Karmen, L. Giuffrida, Nature 201 (1964) 1204.
[37] B. Kolb, J. Bischoff, J. Chromatogr. Sci. 12 (1974) 625.
[38] D.W. Grant, in: D.H. Desty (Editor), Vapour Phase
Chromatography, Butterworths, London, 1957.
[39] S.S. Brody, J.E. Chaney, J. Gas Chromatogr. 4 (1966) 42.
[40] K. Holden, Ph.D. thesis, University of Leeds, 1998.
trends in analytical chemistry, vol. 21, nos. 9+10, 2002
[41] A.J. McCormack, S.C. Tong, W.D. Cooke, Anal. Chem. 37
(1965) 147.
[42] L. Ebdon, S. Hill, R.W. Ward, Analyst 111 (1986) 1113.
[43] B.D. Quimby, J.D. Sullivan, Anal. Chem. 62 (1990)
1027.
[44] H.G.J. Mol, Th. Hankemeier, U.A.Th. Brinkman, LC.GC
Intern. 12 (1999) 108.
[45] C. Gohlke, Anal. Chem. 31 (1959) 535.
[46] M. Novotny, J.M. Hayes, F. Bruner, P.G. Simmonds,
Science 189 (1995) 215.
[47] G. Hammer, B. Holmstedt, R. Ryhage, Anal. Biochem. 25
(1968) 532.
[48] M. van Deursen, J. Beens, H.-G. Janssen, P.A. Leclercq,
C.A. Cramers, J. Chromatogr. A 878 (2000) 205.
[49] D.H. Desty, A. Goldup, B.A.F. Whyman, J. Inst. Petrol 45
(1959) 287.
[50] G. Schomburg, in: R.E. Kaiser (Editor), Proceedings 4th
International Symposium on Capillary Chromatography,
Huethig, Heidelberg, Germany, 1981, p. 371.
[51] P. Sandra (Editor), Sample Introduction in Capillary Gas
Chromatography, Huethig, Heidelberg, Germany, 1985.
[52] K. Grob, G. Grob Jr., J. Chromatogr. 7 (1969) 584.
[53] A. Zlatkis, J.Q. Walker, J. Gas Chromatogr. 1 (1963) 9.
[54] K. Grob, K. Grob Jr., J. Chromatogr. 151 (1978) 311.
557
[55] R. Consden, A.H. Gordon, A.J.P. Martin, Biochem. J. 38
(1944) 244.
[56] J. Beens, J. Blomberg, P.J. Schoenmakers, J. High Resol.
Chromatogr. 23 (2000) 182.
[57] R.E. Majors, J. Chromatogr. Sci. 18 (1980) 571.
[58] K. Grob, B. Schilling, J. High Resol. Chromatogr. 8 (1985) 726.
[59] D.R. Deans, Chromatographia 1 (1968) 18.
[60] G. Schomburg, F. Weeke, in: S.G. Perry E.R. Adlard
(Editors), Gas Chromatography 1972, The Institute of
Petroleum, London, 1972, p. 285.
[61] Z. Liu, J.B. Phillips, J. Chromatogr. Sci. 29 (1991) 227.
[62] J. Beens, U.A.Th. Brinkman, Trends Anal. Chem. 19
(2000) 260.
[63] J. Hooimeijer, A. Kwantes, F. van de Craats, in: D.H.
Desty (Editor), Gas Chromatography 1958, Butterworths,
London, 1958, p. 288.
[64] D.H. Desty, A. Goldup, W.T. Swanton, in: N. Brenner
(Editor), Gas Chromatography, Academic Press, New
York, USA, 1962, p. 105.
[65] T. Lynch, in: A.J. Handley, E.R. Adlard (Editors), Gas
Chromatographic Techniques and Applications, Sheffield
Academic Press, Sheffield, UK, 2001, p. 298.
[66] J.R. Hopkins, I.D. Jones, A.C. Lewis, J.B. McQuaid, P.W.
Seakins, Atmos. Environ. 36 (2002) 3217.