GC
GC
GC
25 mm × 0.25 mm
based upon pressure differences..2/ Constant flow can be
0.8
delivered across a range of pressure drops that may arise
He
0.6 due to changes in temperature but cannot compensate
H2 for changes in barometric pressure. An advance in
0.4 instrumentation during the past decade has been the
commercialization of flow programming so that flows
0.2
may be made highly reproducible.
10 20 30 40 50 60 70 80 90
2.3 Gas Sources and Purity
Average linear velocity (cm s−1)
A common gas source for nitrogen or helium is the pres-
Figure 3 Plot of separation efficiency versus column flow rate. surized cylinder or bottled gas supply, readily supplied as
INSTRUMENTATION OF GAS CHROMATOGRAPHY 3
a steel tank with a two-stage pressure regulator. This is still column. Another complication with syringe injections is
a common gas source though gas generators for nitrogen the introduction of particulate and reactive materials into
(air and hydrogen too) can be commercially competitive columns. Protection is afforded by precolumns. Further
with bottled gas and have advantages in safety. information on syringe injections and the range of options
Regardless of the gas source, special attention must for injection methods can be found in excellent reference
be given to the purity of tubing used to connect the sources..10,11/
source and the gas chromatograph and to impurities in Gas samples can be injected into the column using
the gas supply. Most columns do not tolerate moisture and gas-tight syringes or using rotary gas switching valves
oxygen well when operated at temperatures over 100 ° C. that offer enormous flexibility for GC instruments..12/
Best results for column longevity and chromatographic Precision gas switching valves allow a gas sample to be
reproducibility occur when the carrier gas is cleaned over measured with a precise volume and introduced into
molecular sieve beds (to reduce moisture). In addition, carrier gas flow without interrupting column flow. Sample
specialized traps can be purchased to reduce or remove is loaded into a loop and then, with a change in the
hydrocarbons and oxygen in the carrier gas. valve position, is swept into the column under flow of
the gas source. Heated switching valves such as those
made by VICI, Inc..13/ are also useful in the analysis
3 SAMPLE INLETS of sorbent traps. When traps are heated and switched
in-series with the analytical column, constituents will be
thermally desorbed for GC separations. Switching valves
The chromatographic process begins when sample is
can be automated via electronic actuators and can be
introduced into the column, ideally without disrupting
incorporated into purge-and-trap methods that are useful
flows in the column. The chromatographic results will
for characterizing aqueous samples for volatile organic
be reproducible inasmuch as this is accomplished with
constituents.
a minimum of change in pressure or flow of the carrier
gas or mobile phase. Also, the injection step establishes
the initial (and best possible) peak width for the GC 3.2 Pyrolysis
measurement. Thus, delivery of sample into the column Another inlet option which is now routine in certain
should be controlled, reproducible, and rapid. specific applications of material sciences is that of sample
pyrolysis where solid samples are rapidly heated to a
3.1 Syringes and Switching Valves point of thermal decomposition in a reproducible manner.
At temperatures in excess of 600 ° C, substances such as
A common method for placing samples on a GC column natural or synthetic polymers thermally decompose to
is to use the microliter syringe with a needle to penetrate small molecular weight, stable substances that provide
a plastic membrane. In this method a gas-tight seal is a chromatographic profile which is unique to certain
maintained and sample is deposited into a heated zone. materials. Such an injector enlarges the application
If liquid or solid, sample is volatilized and swept to of GC to solid samples that would not normally
the column and this can be accomplished by manual be considered suitable for GC characterization, and
injections in ¾1 s. Syringe injection is a convenient pyrolysis methods have become standardized for some
and generally effective method though the thermoplastic applications such as assaying plastics. A journal now
septum develops leaks after repeated injections. Fatigue exists for analytical applications of pyrolysis, the Journal
of the plastic septum limits the number of injections of Analytical and Applied Pyrolysis. Attachments to inlets
to ¾30 before the septum must be replaced. A second are commercially available and serve to extend GC in
difficulty arises with impurities from off-gassing or forensic and industrial applications, as shown in Table 1.
decomposition of the septum and these are seen as so-
called ghost peaks or peaks in control blanks..8/ Table 1 Examples of applications of pyrolysis GC
Advances with capillary columns introduced unprece-
dented precision and accuracy to GC measurements and Example Ref.
limitations with syringes became apparent..9/ Discrimina-
Lignin by pyrolysis methylation 14
tion toward high boiling point components was seen with Synthetic polymers
syringe injections and techniques to remedy the failings Fast GC 15
have been developed..9/ Sometimes thermal volatiliza- Bibliography 16
tion may lead to decomposition of samples so efforts Rosin glycerin esters in paper 17
to remove the discrimination and decomposition moti- Chlorinated polyethylene structure 18
Coating materials: bibliography 19
vated the use of so-called on-column injections where Proteinaceous binders in paints 20
sample is deposited directly from the syringe into the
4 GAS CHROMATOGRAPHY
are available.36,37/ and any general text on instrumental near general availability of gas chromatography/mass
analysis will have introductory material on the common spectrometry (GC/MS) instrumentation. In a GC/MS
detectors. A biennial review contains an extensive section analysis, a mass spectrum can be obtained continuously
on developments of GC detectors and can serve as a guide at fixed intervals of ¾0.1 s throughout the analysis. Con-
to primary literature..38/ sequently, a mass spectrum can be obtained for each
chromatographic peak and the shoulders and baselines
in the chromatogram. No other detector can provide
5.1 Detectors
the richness of information available in such results.
Effluent from the column enters a detector where the Detection limits can be enhanced through the use of
composition of the carrier gas stream is characterized single ion monitoring where the mass spectrometer is
through one of several possible chemical or physical prop- used for detecting the intensity of one or a few ions.
erties of molecules. The mainstays in GC have been the This can provide the specificity of a mass spectral
flame ionization detector (FID), the thermal conductivity pattern for response without losses in detection limit
detector (TCD) and the electron capture detector (ECD). associated with scanning over unused m/z space. One
Other commercially available detectors include the pho- revolution in the past decade has been the application
toionization detector (PID), the nitrogen– phosphorus of powerful desktop computers to control instrumen-
detector and the atomic emission detector, though these tation and especially to control data acquisition and
have been less prevalent historically than the FID, TCD, handling.
and ECD. Other detectors have been introduced through
the years but have never become widely used in GC meth- 5.2 Data Systems
ods. The FID relies upon the formation of gaseous ions
from organic molecules combusted in a hydrogen – air At a fundamental level, acquisition of chromatographic
flame; the TCD is based upon changes in the heat absorb- results has been little changed since the early days of
ing properties of the gas effluent when the carrier gas is GC, though the digital revolution has meant that strip
altered with analyte; the ECD response is governed by chart recorders, once the mainstay of collecting chro-
the ability of some molecules to attract and remove ther- matograms, cannot be found today and only electronic
malized electrons. Despite long-standing conventions for recording-integrators or microcomputers are used. Signal
the design and operation of these detectors, advances still from the detector amplifier is digitized and stored to disk
occur. allowing enormous convenience in retrieving and replay-
Examples of evolutionary changes include the small ing results. This means that peak retention times, peak
FID designs.39/ and designs where gas mixing is arranged areas, etc. are automatically reported and have been since
to provide optimum response..40 – 42/ A recurring theme in the mid-1970s. In addition, software allows the results to
advances in ECD has been a nonradioactive alternative be displayed in an automated manner, i.e. reports can be
to the normal source, 10 mCi of 63 Ni. Despite promising generated according to standard reporting formats. All
discoveries, the radioactive source is still the favored this can be economically integrated into the total instru-
choice. The applications of ECD illustrate the advantages ment control and management through computers and is
of selective detectors where analyte can be found in the an option on all chromatographs and a standard feature
presence of potentially interfering matrix. on most instruments.
Examples where the ECD was chosen to detect a
specific chemical family over interfering backgrounds
include: halocarbons in air for oceanographic tracer 6 MINIATURIZED, HIGH-SPEED,
studies;.43/ chlorobutanol in mouse tissues and fluids;.44/ AND PORTABLE GAS
organochlorine compounds in milk products;.45/ pesti- CHROMATOGRAPHS
cides and other organochlorides in water;.46/ organochlo-
rine pesticides in edible oils and fats..47/ One area of GC that has shown vibrancy with advances
In the last two decades, inexpensive mass spectrome- during the 1990s is that of small, fast, and portable GC
ters or mass-selective detectors (MSDs) have dramatically instruments. Though process gas chromatographs were
transformed the practice of GC. Once the purview of amongst the first sophisticated analyzers placed into
laboratories able to sustain the high cost of mass spec- industrial on-site measurements, the subject has taken
trometers and the high level of maintenance, instrument new significance following the burgeoning environmen-
manufacturers made mass spectrometers both robust and tal movement. Making measurements where a sample is
inexpensive. This development, when combined with the located rather than relocating samples to a centralized
appreciation that analytical confidence is highest with laboratory underlies this trend. Recently, a new journal
a mass spectrometer as the detector, has resulted in a has appeared to support these efforts, Field Analytical
6 GAS CHROMATOGRAPHY
Chemistry and Technology, which includes portable GC field portable GC/MS systems can be expected to increase
advances. dramatically.
In high-speed GC, retention times can be pushed under Another sophisticated detector for GC is the ion
a few minutes or seconds with short, narrow bore columns mobility spectrometer and recently it too has been
or high flow rates. Part of the challenge in fast GC is the coupled to gas chromatographs for field analysis..59,60/
compressibility of the carrier gas and the necessary speed The utility of this hand-held gas chromatograph/ion
(low time constants) for subcomponents such as injectors mobility spectrometer analyzer was demonstrated by
and detectors for high-speed separations. rapid screening (¾20 s) with chemical warfare agents
such as dimethyl methylphosphonate..61/ One of the
6.1 Instrument Designs most impressive demonstrations was that from the US
Army where a portable pyrolysis-gas chromatograph/ion
An example of the size possible for small gas chro-
mobility spectrometer was developed for screening
matographs is an ultimate miniature gas chromatograph
airborne pathogens. This unit is shown in Figure 4.
created using silicon micromachining and integrated cir-
This part of GC instrumentation may be expected
cuit processing techniques..48/ This GC analyzer contains
to undergo continued development as interest in speed
a 0.9 m long ð 300 µm wide ð 10 µm high rectangular col-
of analysis pushes dimensions and hardware. Therefore,
umn coated with a 0.2-µm thick liquid phase. The injector
it represents one of the few areas of growth in GC
is a 10-µm-long sampling loop with the same cross-section
instrumentation that can be recognized in the absence of
as the column. Dual detectors based upon a coated
a revolutionary change in GC methods.
chemiresistor and on thermal conductivity are used. The
complete system is packaged in less than 23 cm2 and is
2.5 mm high. Although limited in scope to the detection
of ammonia and nitrogen dioxide, this miniature chro-
matograph offers exciting possibilities for future field
instruments.
One trade-off for high-speed GC is the loss of
capacity due to the smaller diameter and shorter
columns. Application of packed capillary columns in
high-speed GC has been shown to improve capacity
and selectivity.49/ while obtaining high-speed separa-
tion for light hydrocarbons..50/ An alternative is the
multicapillary column which improved capacity while
maintaining the efficiency obtained with small internal
diameter columns..51/
Injection techniques for high-speed GC must provide
narrow bandwidths due to fast analysis time requirements
without compromises in resolution..52/ One means to
accomplish this is through cryogenic inlets which provide
narrow bandwidths.53/ and in some instances injection
times can be shorter than 10 ms..54/
6.2 Detectors
Mass spectrometers might be considered ideal detectors
and adaptations to fieldable gas chromatographs have
been made. One design is the size of a standard
size suitcase, weighs ¾31 kg and uses ¾600 W under
peak loads..55/ Naturally, field portability is a goal
and man-portability has been demonstrated..56/ A cart-
portable unit has been described and was capable
of screening 1000 samples an hour at a speed of
20 – 32 km an hour..57/ Portable GC/MS instruments
were also used for industrial hygiene applications..58/
As the need for field measurements increases and mass Figure 4 Gas chromatograph/ion mobility spectrometer for
spectrometry (MS) becomes miniaturized, the number of bacterial analysis.
INSTRUMENTATION OF GAS CHROMATOGRAPHY 7
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