260
4, 2000
The role of gas chromatography in
compositional analyses in the petroleum
industry
Jan Beens*, Udo A.Th. Brinkman
Vrije Universiteit, Faculty of Sciences, Department of Analytical Chemistry and Applied Spectroscopy,
de Boelelaan 1083, 1081 HV Amsterdam, The Netherlands
Because of the complex character of petroleum
fractions and products, gas chromatography has
played an important role as an analytical technique
in this area since its introduction. For the majority
of oil fractions classifying or group-type analyses
are performed rather than determinations of all
the individual constituents. The general composi-
tion of petroleum is discussed and also the relation
between composition, product properties and
processability. Compositional analyses for petro-
leum products are reviewed, especially in terms of
multi-dimensional gas chromatography. The
important role that comprehensive two-dimen-
sional gas chromatography is expected to play in
the near future in unraveling the composition of oil
fractions is also discussed. z2000 Elsevier
Science B.V. All rights reserved.
Keywords: Oil analysis; Composition of oil fractions;
Multidimensional gas chromatography;
Two-dimensional gas chromatography
1. Introduction
1.1. The composition of petroleum and its fractions
Throughout this article a logical chemical
nomenclature will be used wherever possible.
However, within the petroleum industry, an en-
vironment rich in traditions ( some of which
are very old and are not easily abolished ), there
exists a great deal of inherited nomenclature. This
has evolved with the ¢eld and is therefore neither
logical nor precise. Many petroleum fractions,
products and constituents are designated only
by the way in which they have been generated,
*Corresponding author.
E-mail: beens@chem.vu.nl
0165-9936/00/$ ^ see front matter
PII: S 0 1 6 5 - 9 9 3 6 ( 9 9 ) 0 0 2 0 5 - 8
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trends in analytical chemistry, vol. 19, no.
or by operational procedures. To some extent,
we must live with these inherited terms, even
though they are often vague and sometimes mis-
leading.
For example, petroleum fractions were originally
classi¢ed as `light', `middle' and `heavy' materials on
the basis of their density. Because density and boil-
ing range frequently go hand in hand, these terms
became interchangeable with low ( 0^150³C ),
medium ( 150^370³C ) and high boiling points
( s 370³C ). However, some highly aromatic light
fractions may have a higher density than some
highly paraf¢nic middle distillate fractions. Simi-
larly, some highly aromatic middle distillate frac-
tions may have a higher density than some highly
paraf¢nic heavy fractions.
The inherited terms used in this paper are
marked with an asterisk (*) and clari¢ed in the glos-
sary.
1.1.1. Occurrence of different types of compounds in
petroleum
The constituents of petroleum and its fractions
can be classi¢ed into two major compound groups,
the hydrocarbons and the hetero-compounds.
Hydrocarbons only contain carbon and hydrogen;
hetero-compounds also contain sulfur, nitrogen,
oxygen, vanadium, nickel or iron. The general for-
mula is Cn H2n‡z Xa Yb Zc , in which X, Y and Z are
hetero-atoms, z is the de¢ciency value of hydrogen,
and a, b and c are the number of hetero-atoms.
The hydrocarbons can be subdivided into the
following group types:
1. Acyclic alkanes ( also called paraf¢ns ),
branched or normal ( also called iso- or nor-
mal ). General formula: Cn H2n‡2
2. Cyclic alkanes ( also called naphthenes ).
These contain one ( mono-naphthenes ) or
more ( poly-naphthenes ) saturated ( or naph-
ß 2000 Elsevier Science B.V. All rights reserved.
trends in analytical chemistry, vol. 19, no. 4, 2000
thenic ) rings. They may have one or more
( branched ) paraf¢ns attached to the ring.
Naphthenic rings contain either ¢ve or six car-
bon atoms. General formula: Cn H2n for mono-
naphthenes; CnH2n32 for di-naphthenes;
Cn H2n34 for tri-naphthenes; etc.
3. Alkenes ( also called ole¢ns ), branched, nor-
mal or cyclic. Crude oils and products derived
directly from crudes through distillation
( straight-run products ) in general do not con-
tain ole¢ns. Processed products, especially
those obtained by thermal or catalytic crack-
ing, may contain large quantities of ole¢ns.
General formula: Cn H2n for mono-ole¢ns;
Cn H2n32 for di-ole¢ns or naphthenic mono-
ole¢ns; etc.
4. Aromatics ( containing at least one benzene
ring ). They may have one or more paraf¢ns
or naphthenes attached to the ring. Molecules
containing one benzene ring are classi¢ed as
mono-aromatics, those with two aromatic
rings as di-aromatics, etc. General formula:
Cn H2n36 for mono-aromatics with alkyl substi-
Fig. 1. The number of possible hydrocarbon isomers.
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261
tution; Cn H2n38 for mono-aromatics with one
naphthenic ring; etc.
The hetero-compounds are classi¢ed according
to the hetero-atom in the molecule.
1. Sulfur compounds. These are usually present
in higher concentration than the other hetero-
compounds. Their occurrence in petroleum
products is undesirable for various reasons.
Most of the sulfur compounds, especially
hydrogen sul¢de and the mercaptans, are
very malodorous. Even minor amounts of sul-
fur may have detrimental effects on catalysts
used in conversion processes. If the product is
used as a fuel, the sulfur will be converted into
SO2 and SO3 , which are harmful to the envi-
ronment. The sulfur compounds can be sub-
divided into:
1.1. thiols ( also called mercaptans ), R^S^H, with R
being an alkyl substituent.
1.2. sul¢des, R^S^RP, and disul¢des, R^S^S^RP.
262 trends in analytical chemistry, vol. 19, no. 4, 2000

Fig. 2. The number of possible sulfur-containing isomers.

1.3. thiophenes, R^C4 H3 S, benzothiophenes, R^ or salts [ 3 ]: naphthenic acids, phenols, fatty

C8 H5 S, dibenzo-thiophenes, R^C12 H7 S and acids, furans and phenyl ketones.
benzonaphthothiophenes, R^C16 H9 S. 4. Metal-containing compounds. Vanadium,
nickel and iron are present in very low con-
2. Nitrogen compounds. Although they are gen-
erally present in lower concentrations than the
Table 1
sulfur compounds, basic nitrogen compounds
Carbon number, boiling points and number of possible paraf¢n
are notorious catalyst poisons, when using isomers
acidic proton-donor catalysts. The nitrogen
compounds can be subdivided into: Carbon Boiling point n-alkane Number of
number (³C ) isomers
2.1. basic compounds such as pyridines, quino- 5 36 3
lines, benzoquinolines and azacarbazoles 8 126 18
[ 1,2 ]; 10 174 75
2.2. neutral or weakly basic (= non-titrable ) com- 15 271 4347
20 344 3.66U105
pounds such as pyrroles, indoles, carbazoles,
25 402 3.67U107
amides [ 2,3 ] and porphyrin-type compounds; 30 450 4.11U109
2.3. acidic compounds such as hydroxypyridine- 35 490 4.93U1011
and indole-carboxylic acids [ 4 ]. 40 525 6.24U1013
45 554 8.22U1015
Oxygen compounds. There are ¢ve groups of 60 620 2.21U1022
3.
80 678 1.06U1031
oxygen compounds, some of which can be 100 715 5.92U1039
present in the form of their respective acids

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trends in analytical chemistry, vol. 19, no. 4, 2000
Fig. 3. Schematic integrated oil-re¢ning con¢guration.
centrations in organic metal complexes. The
most common types of complexes present are
porphyrins.
1.1.2. The number of compounds in petroleum
Petroleum fractions are among the most complex
samples an analyst can face in terms of the number
of compounds present. Even more challenging
is the fact that, unlike the situation with other com-
plex samples in which only a few speci¢c com-
pounds have to be separated from the matrix, in
petroleum the matrix itself usually must be sub-
jected to separation and analysed. Table 1 shows
the number of possible paraf¢nic isomers per car-
bon number [ 5,6 ] and the boiling point of the
n-alkane [ 7 ].
Table 1 shows the number of possible isomers
only in the simplest type of compound. Figs. 1
and 2 present extrapolations of the number of pos-
sible isomers of all the hydrocarbon and sulfur com-
pounds possibly present in petroleum fractions
well below a carbon number of 20. This extrapola-
tion was performed from the theoretically possible
TRAC 2616 14-3-00
263
number of isomers. Even if only a few per cent of all
possible compounds are actually present, the num-
bers are overwhelming. This makes a complete
compositional analysis of the higher-boiling frac-
tions impossible. The analysis of petroleum ( frac-
tions ) is therefore focused on classi¢cation.
1.2. Oil processing and process modelling
Its origin and geological history determine the
composition of a crude oil, and crudes vary widely
with respect to boiling range and chemical charac-
teristics. Primary oil processing ( distillation, extrac-
tion and conversion processes ) rarely results in
product packages which match local demands.
Crude oils in general contain a surplus of heavy
fuel and insuf¢cient middle distillates and gasoline,
whereas the demand for light products has
increased in the last two decades and is still increas-
ing. Although the feedstocks that are processed
almost directly re£ect the crude origin, blending
options of the intermediate products only indirectly
link the re¢ning sections. Fig. 3 illustrates the com-
plexity of modern integrated oil re¢ning.
264
Fig. 4. Characterisation of oil fractions.
Oil processes vary considerably in type of feed-
stock, conditions and catalytic or thermal nature,
and they perform a variety of re¢ning jobs ranging
from sulfur reduction in hydrotreating, octane num-
ber* improvement in catalytic reforming to ( hydro )
cracking of heavy feedstocks into light distillates
and gases. In spite of these differences, on a molec-
ular basis oil processes share the same small num-
ber of basic reaction types. This principle has been
used to develop general models suitable for all oil
processes. The basic characteristics that determine
the conversion processes are, apart from kinetic
properties, the chemical nature of the hydrocar-
bons in terms of paraf¢nic, ole¢nic, naphthenic
and aromatic carbon as well as the amount of het-
ero-atoms [ 8 ].
Conventional product properties and speci¢ca-
tions, such as octane number, cetane number* and
smoke point* are directly calculated from the chem-
ical composition as a function of boiling point [ 9 ].
Fig. 4 shows the relationship between the chemical
structures and these derived product properties. In
view of the changing local demands for light prod-
ucts and growing environmental concern, which
calls for cleaner oil products and processes, the
re¢nery scene is continuously changing. Legislative
measures tighten the quality constraints of oil prod-
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trends in analytical chemistry, vol. 19, no. 4, 2000
ucts in terms of lower sulfur and aromatic content.
Detailed structural information of crude oil and oil
products in terms of paraf¢nic, ole¢nic, naphthenic
and aromatic carbon and hetero-compounds is,
therefore, becoming increasingly important and
investing in the development of analytical tools
that can provide or improve this information is a
necessity.
1.3. The analysis of petroleum
Already in the early days of petroleum re¢ning,
analyses were performed in order to characterise
the products. Most of these ( generally physical )
measurements comprised a product property, the
most common one being the boiling range. The
determination of density, refractive index (RI ), vis-
cosity, £ash point* and the cold-£ow properties*,
such as pour point* and cloud point*, were also
popular. These analyses are still performed in all
re¢nery laboratories. Compositional analyses
were also performed with remarkable dedication.
In the late 1920s, the American Petroleum Institute
started a project ( API Research Project 6, `The Sep-
aration, Identi¢cation and Determination of the
Chemical Constituents of Commercial Petroleum
Fractions') to isolate individual hydrocarbon spe-
trends in analytical chemistry, vol. 19, no. 4, 2000 265

Plate 1. The state-of-the-art of chromatography in the petroleum ¢eld.

The area indicated as mare vacui is an empty area, which does not contain any compounds. Two-ring aromatics have at least 10, three-
ring aromatics at least 13, four-ring aromatics at least 16 carbon atoms, etc. The polars are assumed not to have carbon numbers
below 25.

cies from crude petroleum, in order to determine
their physical properties. They used ( azeotropic )
distillation, extraction, crystallisation and adsorp-
tion to isolate the compounds. The result of this
immense work was published in 1953 [ 10 ]. All
204 individual hydrocarbons containing from ¢ve
to nine carbon atoms were isolated and their boiling
point, density, refractive index and freezing point
were reported.
Today, structural group analyses, which provide
information on the composition of petroleum frac-
tions and products, are generally instrumental anal-

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266 trends in analytical chemistry, vol. 19, no. 4, 2000

The map of the petroleum ¢eld.

Although compositional analysis in the oil industry has been with us for over a century, the composition of a signi¢cant part of
petroleum and its products is still unknown. Analogous to the cartographers in the 16th and 17th centuries, many petroleum
technologists ¢ll the gaps of terra incognita of the oil ¢eld with surmises and assumptions. The ¢gure presents a state-of-the-art map of
the petroleum ¢eld.
The borders between the different compound classes in petroleum ( ole¢ns, paraf¢ns, naphthenes, mono- and di-aromatics, poly-
aromatics and polars ) are depicted as solid lines. These turn into dashed lines in the higher-molecular-mass regions where all
compounds are likely to contain some saturated groups, some naphthenic groups, one or more aromatic groups, and possibly one or
more hetero-atoms. It then obviously becomes impossible to unambiguously de¢ne the nature of the different compounds in terms
of structural groups. It may be argued that, for the same reason, a physical separation technique such as ( gas ) chromatography will
fail to provide structure-based resolution in this area.
For compounds with fewer than ¢ve carbon atoms, including the permanent gases, various quantitative gas analysis methods exist,
some of which are still based on the use of GC packed columns. GC can perform the quantitative analysis of all individual compounds
with four to six carbon atoms. The individual saturates and aromatics can be analysed quantitatively up to nine carbon atoms. For up
to about 12 carbon atoms, instruments such as the PIONA analyser allow quantitative group-type analyses of all compound classes
by carbon number. GCUGC in principle allows the quantitative analysis of a large number of individual compounds generally and of
all group types of fractions with carbon numbers up to 30. With SFC or LC methods, quantitative group-type separations into
aromatics and non-aromatics can be performed for compounds with up to 20^25 carbon atoms. Above that number no quantitative
compositional analytical procedures are available for the total oil sample.
6

yses. These comprise nuclear magnetic resonance
(NMR ), mass spectrometry (MS ), and infrared spec-
troscopy ( IR ) and various chromatographic tech-
niques. Among the instrumental techniques, gas
chromatography ( GC ) has become the most impor-
tant analytical technique in the oil industry. It will
be covered extensively in Section 2.
Among the spectroscopic techniques, NMR has
gained the most prominent place in the composi-
tional analysis of petroleum fractions. A review by
Snape et al. [ 11 ], and papers by Bartle et al. [ 12 ],
Cookson et al. [ 13 ] and Netzel [ 14 ] discuss the use
of 1 H-NMR for the compositional analysis of petro-
leum fractions. 13 C-NMR has also been applied to
the compositional analysis of petroleum fractions
[ 12,15,16 ].
In the mass spectrometric techniques (MS ), non-
fragmenting MS techniques using `soft ionisation'
are generally preferred for compositional analyses,
since they produce much simpler spectra. Field ion-
isation ( FIMS ) is the most attractive option, because
it produces almost fragmentation-free spectra. Var-
ious authors have reported methodologies for the
MS-based compositional analysis of hydrocarbons
[ 17^19 ]. Recently supersonic jet-MS has become a
new candidate, since it produces ^ next to classical
electron-impact patterns ^ a large abundance of
molecular ions [ 20 ].
IR spectroscopy is mainly used for the determi-
nation of nitrogen- and oxygen-containing groups
in petroleum. McKay et al. [ 21,22 ] used IR for deter-
mining the acids and bases in high-boiling petro-
leum fractions. Jacobson et al. [ 23 ] determined dif-
ferent oxygen-, sulfur-, and nitrogen-containing
compounds with IR.
2. The role of gas chromatography in the
oil industry
2.1. General
As already pointed out in Section 1.1.2, the num-
ber of possible constituents of petroleum ( prod-
ucts ) is so immense that no single-column tech-
nique can separate all of them. Even state-of-the-
art capillary columns, with peak capacities of 1000
and more, are unable to do so. An illustration is
given in Fig. 5, a separation of a light fraction of a
catalytically cracked product on a 50 m, 0.25 mm
i.d. capillary column. The ¢nal boiling point of the
sample is 150³C, which means that only com-
pounds containing fewer than 10 carbon atoms
are present. However, even in the range of the
C6 s, with their 28 isomers ( 7 saturated and 21 ole-
¢nic ), co-elution is seen to occur.
For that reason multi-dimensional GC was intro-
duced as a means to effect better separation of com-
plex mixtures. The technique was already explored
in the late 1950s for chlorinated hydrocarbons by
using two packed columns and it was designated
two-stage chromatography [ 24,25 ]. A fully inte-

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trends in analytical chemistry, vol. 19, no. 4, 2000
Fig. 5. Capillary column separation of a catalytically cracked light product. ( Courtesy D. Grutterink, Analytical Controls B.V. )
grated system for the complete analysis of all the
constituents of a re¢nery off-gas using four different
columns was presented in 1959 by Bloch [ 26 ].
A rather elegant way of switching between differ-
ent coupled columns in a multi-dimensional system
was presented by Deans [ 27,28 ], who used pres-
sure differences instead of valves to switch £ows
between the columns. The main advantage of this
approach is that the sample components do not
have to pass any valves and that adsorption on
valve seats, etc. is consequently prevented.
Since 1960 the number and variety of multi-
dimensional (= multi-column ) GC systems have
steadily increased [ 29 ]. The ¢nal development in
this area has been the introduction of the PIONA
analyser in 1971 [ 30 ], with PIONA standing for par-
af¢ns, iso-paraf¢ns, ole¢ns, naphthenes and aro-
matics. This system exploited the unique separation
of naphthenes and paraf¢ns by carbon number on a
column packed with zeolites of a very speci¢c pore
size ( molecular sieves 13X ) [ 31 ]. In later years it
was extended to include samples having boiling
points up to 270³C [ 32 ] and implemented in a com-
mercial instrument [ 33 ], which is still in use in the
majority of re¢nery laboratories for the composi-
TRAC 2616 14-3-00
267
tional analysis of gasolines and naphthas. A sche-
matic diagram of the separation system is shown in
Fig. 6.
A chromatogram that can typically be obtained
with this set-up is presented in Fig. 7. Since all com-
ponents of the injected sample eventually reach the
detector, quantitation can be performed by internal
normalisation, using FID response factors for the
different groups.
The PIONA method can be used to analyse
hydrocarbon samples ( gasolines and naphthas )
from propane through dodecane ( boiling point,
216³C ). An extension up to pentadecane ( boiling
point, 271³C ) is possible, but only for the separa-
tion of naphthenes and paraf¢ns. The upper limit of
the procedure is set by the separation on the molec-
ular-sieve column. In order to elute still higher-boil-
ing compounds from such a column, it must be
heated to temperatures far above 400³C, and ther-
mal degradation of the sample compounds may
occur.
Other multi-dimensional systems have been
reported that use the `heart-cut' approach. A part
of the ef£uent of the ¢rst column is introduced,
after ( cold ) trapping and re-injection, into a second
268
Fig. 6. Schematic diagram of the PIONA analyser. OV-275 = polar column, OV-101 = non-polar column, trap = Tenax trap, Pt = hy-
î = n-alkane trap, 13X = molecular sieve 13X column, V = valve.
drogenator, 5 A
column with different characteristics, which sepa-
rates this rather small part of the sample. Schoen-
makers et al. [ 34 ] reported the analysis of low con-
centrations of phenol in a catalytically cracked
product with such a heart-cutting technique. The
two chromatograms, with the upper one represent-
ing the ¢rst separation on a non-polar column, and
the lower one the heart-cut on a polar column, are
shown in Fig. 8. Van den Bosch [ 35 ] presented a
heart-cut separation of some individual C9 and C10
mono-aromatics from a whole crude oil. The sepa-
rated compounds were used as ¢ngerprinting com-
pounds to establish the origin of the crude oils.
Although the heart-cut technique allows a
unique separation, the separation achieved in the
¢rst column is partly destroyed by the focusing
effect in the trapping device. More importantly,
only a small part of the ¢rst separation is used,
and the rest of the ¢rst-column chromatogram is
disregarded. In view of the discussions below, it is
useful to indicate such two-dimensional chroma-
tography as non-comprehensive.
Combining different chromatographic tech-
niques increases the number of possibilities of a
multi-dimensional system. One of the ¢rst exam-
ples was presented by Stahl [ 36 ], who described
the coupling of supercritical £uid extraction
(SFE ), using supercritical CO2 as the extraction
£uid, and thin-layer chromatography (TLC ) by
means of an automatic deposition system. He pre-
sented a number of possible applications of the
system. The coupling of SFE or column liquid chro-
matography ( LC ) to GC opened a new area of
powerful separation systems. Reviews of coupling
techniques as given by Davies et al. [ 37,38 ] and
Munari et al. [ 39 ] are directed at the coupling of
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trends in analytical chemistry, vol. 19, no. 4, 2000
LC and GC and its applications. Although such sys-
tems are very powerful in terms of selectivity and
resolution, only few have been reported as appli-
cable to the petroleum ¢eld [ 40,41 ]. None of these
systems, however, yielded a full compositional
analysis of the fractions analysed, i.e. they are
non-comprehensive.
A fully quantitative compositional analysis of
middle distillates by means of LC^GC hyphenation
was described by Beens et al. [ 42 ]. Column liquid
chromatography, with its high selectivity, and high-
resolution gas chromatography, with its high
resolving power, were coupled on-line ( LC^GC ).
The LC system separates the sample into hydrocar-
bon groups, which subsequently are completely
transferred to the GC for further separation. An
uncoated pre-column accomplishes a `solvent
effect', which enables refocusing of the low-boiling
solutes in the fractions. An early solvent vapour exit
is used to expel the main part of the solvent. Middle-
distillate products such as heavy naphtha, kero-
sene, jet fuel, diesel fuel and light and heavy gasoil
can be characterised quantitatively with such a
hyphenated system.
The same LC^GC system, but now combined
with a sulfur-speci¢c sulfur chemiluminescence
detector (SCD ), was used for the quantitative
group-type analysis of sulfur species in oil fractions
[ 43 ]. Inserting an adapted FID between the GC col-
umn outlet and the inlet of the SCD, to oxidise both
the large amount of hydrocarbons and the low con-
centrations of sulfur species, enables the quantita-
tive characterisation of the sulfur-containing com-
pounds in middle distillates.
As another interesting coupling technique, Blom-
berg et al. [ 44 ] described the coupling of size exclu-
trends in analytical chemistry, vol. 19, no. 4, 2000 269

Fig. 7. Chromatogram of light naphtha separated with the PIONA analyser. The identi¢cation of the various peaks is given in Table 2.
( Courtesy: D. Grutterink, Analytical Controls B.V. )

sion chromatography (SEC ) and GC for the analysis
of a series of additives in a polymeric matrix. The
SEC separation was used as a sample clean-up step
to isolate the additives from the matrix. Even more
complicated is the coupling of SEC, normal-phase
liquid chromatography (NPLC ) and GC for the
characterisation of restricted ( according to size )
and selected ( according to polarity ) fractions of
long residues* [ 45 ]. The seemingly incompatible
separation modes, SEC and NPLC, are coupled
using an on-line solvent evaporation step. Another
complex system, which features the coupling of
£ow injection analysis ( FIA ), LC and GC, was
recently reported [ 46 ]. It allows the determination
of the total amount of potentially carcinogenic
polycyclic aromatic compounds (PACs ) in bitu-
men* and bitumen fumes.
2.2. Comprehensive two-dimensional gas
chromatography
The heart-cut technique can also be performed
on such small fractions of the ¢rst separation that
they only comprise part of a single peak. If such
small cuts are continually made to include all
peaks eluted from the ¢rst column, and these are

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270 trends in analytical chemistry, vol. 19, no. 4, 2000

Fig. 8. Heart-cut separation of low concentrations of phenol in a catalytically cracked product. ( Courtesy: LC-GC International )

Table 2
Group-type identi¢cation of Fig. 7

C-number Peak numbers

saturates ole¢ns aromatics

straight branched cyclic straight branched cyclic

4 17 1 ^ 47 32 ^ ^
5 18 3 2 48 34 33 ^
6 19 5 4 49 36 35 27
7 20 7 6 50 38 37 28
8 21 9 8 51 40 39 29
9 22 11 10 52 42 41 30
10 23 13 12 53 44 43 31
11 24 15 14 54 45a 32
12 25
a
This group contains branched and naphthenic C11 species, which are not separated.

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trends in analytical chemistry, vol. 19, no. 4, 2000
Fig. 9. Schematic of the thermal modulator in a comprehensive 2D-GC system. 1, PTV injector, 2. ¢rst dimension column, 3. heated
slit of the modulator, 4. motor drive of the modulator, 5. micro press ¢t connections, 6. modulator capillary, 7. second dimension
column, 8. FID, 9. column oven.
subsequently focused and re-injected on a second
column with different separation characteristics, a
truly `comprehensive multi-dimensional' separa-
tion will be the outcome. Although technically an
extension of the heart-cut procedure, it is funda-
mentally a new separation technique, provided
that the two separations can be made truly in-
dependent. Since the cuts are very small, they will
contain compounds with several closely similar
characteristics. Only if the second separation is
based on manipulating another characteristic can
these compounds be separated.
The ¢rst comprehensive multi-dimensional sys-
tem was described by Bushey and Jorgenson [ 47 ].
They coupled ion exchange and size exclusion LC
by means of two sample loops mounted on an
eight-port valve. The loops were switched one
after the other to transfer small cuts from the ion
exchange to the size exclusion column, thus allow-
ing a continuous £ow in the ¢rst column. Liu and
Phillips [ 48 ] ¢rst demonstrated comprehensive
multi-dimensional GC. Two GC columns with dif-
ferent retention characteristics were coupled by
means of a thermal desorption modulator, which
was constructed from a gold-painted capillary. A
TRAC 2616 14-3-00
271
constant-voltage power supply provided the cur-
rent to heat the capillary for the thermal desorption
of the trapped fractions. Electrically conductive
paint provides an excellent thermal contact with
the column, while adding very little thermal mass
[ 49 ]. Although good results were obtained with
these thermal modulators [ 50 ], they were not very
robust and had to be replaced frequently. A more
robust and elegant system for thermal modulation
in a comprehensive two-dimensional GC system
was presented more recently [ 51 ] and is depicted
in Fig. 9.
The revolving thermal modulator, called the
sweeper, heats the modulation capillary by moving
rapidly across it. The rapid heating causes the ana-
lytes to evaporate and travel ahead of the modula-
tor movement until they are refocused.
The application of this system to the composi-
tional analysis of oil fractions has been reported
[ 52 ]. An example of a contour plot representing
separation of a gasoil* is depicted in Fig. 10. Since
it provides a separation power which is equal to the
product of the separation powers of the two indi-
vidual columns, the authors denoted the technique
as GCUGC, a term which is now widely accepted.
272 trends in analytical chemistry, vol. 19, no. 4, 2000

Fig. 10. Contour plot of a GCUGC separation of a heavy gasoil. 1, benzene, 2. toluene, 3. ethylbenzene+para+meta-xylene, 4. ortho-
xylene, 7^13. C9 aromatics, 15. C10 mono-aromatics, 16. C11 mono-aromatics, 23. naphthalene, 24. 2-methylnaphthalene,
25. 1-methylnaphthalene, 27. C2 naphthalenes, 28. C3 naphthalenes, 29. C4 naphthalenes, 30^41. n-C8 through n-C19 .

Apart from this separation power, GCUGC offers a
high ordering of the separated species in the two-
dimensional plane. To give an example, the di-aro-
matics in Fig. 10 are not only separated from the
saturates and mono-aromatics, but are grouped in
a band from which more chemical information can
be extracted. Clearly, the different groups of di-aro-
matics, naphthalene (No. 23 ), the methylnaphtha-
lenes (Nos. 24 and 25 ), the naphthalenes substi-
tuted with two carbon atoms (No. 27 ), with three
carbon atoms (No. 28 ) and with four carbon atoms
(No. 29 ) are easily recognised.

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trends in analytical chemistry, vol. 19, no. 4, 2000
Fig. 11. Schematic of the cryo-modulator in a GCUGC system. 1. PTV injector, 2. ¢rst-dimension column, 3. column connection,
4. second-dimension column, 5. FID, 6. moving cryo-modulator, 7. column oven.
Other authors [ 53,54 ] discussed the use of quan-
titative analysis with GCUGC and presented a
model [ 55 ] to predict the ¢nal separation of a
GCUGC system.
Meanwhile, other ways to modulate narrow frac-
tions from the ¢rst dimension into the second
dimension have been reported. Kinghorn et al.
[ 56,57 ] described a device that does not use ther-
mal modulation, but cryogenic focussing ( Fig. 11 ).
The modulator consists of a moving cryogenic trap
and is therefore designated a longitudinal modulat-
ing cryogenic system ( LMCS ). Since this acronym
may easily create confusion with the well-known
LC^MS, we will designate it a cryo-modulator
instead. The ef£uent from the ¢rst column is
retained in a very narrow band inside the cryo-
modulator. Every few seconds the modulator is
shifted from the T ( trap ) to the R ( release ) position.
In the R position, trapped fractions will be released
immediately and start to be subjected to separation
as a narrow band held on the head of the second
column. Meanwhile, ef£uent from the ¢rst column
will be trapped, thus preventing interference with
the chromatographic process of the previous frac-
tion. After a few seconds ( the modulation time ) the
process will be repeated, until the end of the ¢rst-
column GC run. Two-dimensional separations
TRAC 2616 14-3-00
273
quite similar to heat-modulated GCUGC separa-
tions have been demonstrated [ 58,59 ].
A major advantage of the cryo approach is that
the capillary in which the compounds are retained
has to be heated up to the normal oven temperature
only. This makes the system applicable to samples
with much higher ¢nal boiling points than the
Sweeper system can handle. An obvious disadvant-
age is the physical state of the stationary phase at
temperatures that can easily be as low as 350³C.
A comprehensive review on the state of the art of
GCUGC is presented in [ 60 ].
3. Perspectives
Gas chromatography has been used in the oil
industry since it was invented some 40^50 years
ago. Although it is a mature technique with an
excellent track record, there are still intriguing
new developments. One of these is GCUGC
which can provide dramatic peak capacities and,
equally important, structured ( ordered ) chromato-
grams. This facilitates the interpretation of the pat-
terns of oil and oil product samples, especially after
a more general acceptance of and increasing expe-
rience with the technique.
274
As GCUGC is a very young technique and only
one type of instrument is commercially available
( using the Sweeper as a modulator ), much research
will still have to be conducted. This research should
be focused on selection of the preferred type of
modulator and optimisation of its design, develop-
ing and validating protocols for optimum separa-
tion conditions and performing quantitative analy-
ses. As the limited number of present-day users will
undoubtedly con¢rm, increased robustness and
user-friendliness will be important aspects, as will
be the development of proper data-handling tech-
niques. It is one thing to construct impressive 2D
plots; it is quite another matter to carry out the pro-
¢le recognition or comparison.
4. Glossary of inherited terms
Term Explanation
Gasoline fraction ( whether straight-run, processed or
blended ) boiling between 10³C and 200³C
Naphtha fraction ( whether straight-run, processed or
blended ) boiling between 110³C and 190³C
Kerosene fraction ( whether straight-run, processed or
blended ) boiling between 190³C and 290³C
Diesel fraction boiling between 210³C and 340³C, to
be used as a fuel in diesel engines
Light gasoil fraction ( whether straight-run, processed or
blended ) boiling between 250³C and 350³C
Heavy gasoil fraction ( whether straight-run, processed or
blended ) boiling between 340³C and 440³C
Fuel oil mixture of short residue* and gasoil to be used
as a fuel in marine engines. The gasoil is added
to decrease the viscosity of the fuel
Asphaltenes ( high-molecular-mass and highly aromatic )
fraction of residual products that is not soluble
in a light n-alkane, but does dissolve in toluene
Maltenes ( high-molecular-mass ) fraction of residual
products that dissolves in a light n-alkane
Bitumen high-boiling `crude oil', lacking low-boiling
fractions and containing high concentrations
of hetero-compounds
Resins fraction of maltenes extracted from an adsorb-
ent by desorption with a polar solvent
Residue long residue*, short residue*
Long residue residue after atmospheric distillation of a crude
oil ( s 370³C )
Short residue residue after vacuum distillation ( s 550³C )
Octane number measure for the combustion behaviour of a fuel
in a spark-ignition engine. The standard, 2,2,4-
trimethylpentane ( iso-octane ), yields an
octane number of 100
Cetane number measure for the combustion behaviour of a fuel
in a diesel engine. The standard, n-hexadecane
( cetane ), yields a cetane number of 100
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trends in analytical chemistry, vol. 19, no. 4, 2000
Flash point temperature at which, after heating, the vapour
above a petroleum fraction in a closed cup can
be ignited with an open £ame
Smoke point measure for the combustion behaviour of ker-
osenes in an open £ame. The smoke point is a
yardstick for the aromaticity
Cold-£ow viscosity, viscosity index*, pour point*, cloud
properties point*
Viscosity index measure for the change of the viscosity of an oil
fraction with temperature
Pour point temperature at which, after cooling, a liquid oil
fraction solidi¢es
Term Explanation
Cloud point temperature at which, after cooling, the ¢rst
crystals appear in a liquid oil fraction
Depentanise removal ( by distillation ) of the low-boiling
( 6 35³C ) part of a fraction
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