ISSN 0020-1685, Inorganic Materials, 2009, Vol. 45, No. 14, pp. 1593–1597. © Pleiades Publishing, Ltd., 2009.

Original Russian Text © Z.A. Temerdashev, I.A. Kolychev, 2009, published in Zavodskaya Laboratoriya. Diagnostika materialov, 2009, Vol. 45, No. 14, pp. 4–8.

Study and Analysis of Gasolines Modified

during Evaporation and Burning
Z. A. Temerdasheva and I. A. Kolychevb
a
Kuban State University, Stavropol’skaya ul. 149, Krasnodar, 350040 Russia
b Krasnodar Forensic Examination Laboratory, ul. Luzana 38, Krasnodar, 350051 Russia
Received November 28, 2007

Abstract—A technique for determining the traces of gasolines undergoing radical changes owing to evapora-
tion and burning based on normal-phase high-performance liquid chromatography (HPLC) with spectrophoto-
metric detection in the UV spectral range was described. The possibility of differentiating traces of evaporated
and burned gasolines over the composition of aromatic compounds was shown. A parameter of the relative con-
centration of condensed alkylarenes was experimentally obtained, which allows high-reliability identification
of traces of gasolines for internal combustion engines in afterfire residues against the background of pyrolysis
products of carrier objects and other petroleum products. The determined systematic feature associated with the
specificity of the component composition of aromatic hydrocarbons of different petroleum products was
explained
DOI: 10.1134/S0020168509140155

In analytical practice of forensic examination, it is
often necessary to solve the problem of traces of
inflammable petroleum product in afterfire residues.
This is because inflammable petroleum products such
as automobile gasolines and diesel fuel are most com-
monly used as burning initiators in the case of arsons.
It is most difficult to detect traces of gasolines modified
in evaporation and burning processes owing to loss of
most of their diagnostic features. Therefore, in most
cases, it is not only difficult to perform identification,
but also it often seems impossible to establish the fact
of the presence of traces of such petroleum product. An
especially difficult problem is the determination of
traces of modified gasoline against the background of
other distillate petroleum and pyrolysis products
formed under conditions of fires.
In techniques applied to determine petroleum prod-
ucts in environmental objects [1, 2], gas chromatogra-
phy with flame ionization and mass selective detection
is preferred among a broad set of employed methods. In
this case, versions of analyses of gasoline and middle
distillate petroleum products subjected to only partial
evaporation are considered. However, such techniques
are inapplicable to analyze petroleum products modi-
fied under conditions of fires and undergoing more rad-
ical changes in the component composition, at which
the largest fraction of hydrocarbons is lost, up to their
total disappearance. In most cases, it seems impossible
to detect traces of burned gasolines by methods conven-
tionally used in criminal investigation (gas-liquid chro-
matography (GLC), thin-layer chromatography (TLC),
UV and IR spectroscopy).
In currently used techniques for determining petro-
leum product traces [3], it is indicated that differentia-
tion of gasolines and middle distillate petroleum prod-
ucts is possible until the instant at which a sample under
study contains a few percent of paraffins C13H28 and
C14H30. The technique used in criminal investigation
allows the determination of the presence of traces of
modified petroleum products; however, there remain
problems associated with determination of the type of
petroleum products detected in afterfire residues.
The goal of this paper is to study and develop a tech-
nique for determining traces of gasolines modified in
evaporation and burning processes using the normal-
phase HPLC version.
The study was performed using a Milichrom 5-3
chromatograph with an UV spectrophotometric detec-
tor with simultaneous detection at five wavelengths
(210, 220, 230, 240, and 254 nm). Thermally activated
analytical chromatographic columns [4] 2 mm in diam-
eter filled with Silasorb-600 sorbent were used. Ultra-
pure-grade hexane dried by metal sodium was used as
an eluent and for sample preparation. The eluent flow
rate through a column was 100–120 μl/min. Chromato-
grams were measured and processed using the
WINCHROM-1.52 hardware–software system devel-
oped by the Kripton Company (Orel, Russia). The com-
position of fractions of aromatic hydrocarbons of petro-
leum products extracted by semipreparative separation
using a liquid chromatograph was determined using a
Hewlett Packard JCD plus gas chromatography mass
spectrometer with mass spectra library v. 1.0.0.12. Gas
chromatograms of petroleum products under study

1593
1594 TEMERDASHEV, KOLYCHEV
P2
254 nm
P3
h1
P1 254 nm
230 nm
P4
h4 220 nm
210 nm
Fig. 1. Chromatogram of evaporated automobile gasoline:
h2 and h3 are heights of multiplets corresponding to alkyl
derivatives of naphthalene and preferentially to alkyl deriv-
atives of phenanthrene and anthracene; P1 is the peak cor-
responding to phenanthrene, anthracene, and pyrene; P2–
P4 are the peaks corresponding to mono-, di-, and trimethyl
derivatives of phenanthrene and anthracene and methyl
derivatives of fluorine.
were measured using a Hewlett Packard-6890 chro-
matograph with a flame ionization detector.
An analysis of traces of gasolines modified during
evaporation and under fire conditions showed that poly-
cyclic aromatic structures entering into their composi-
tion are less subjected to qualitative and quantitative
modifications [5]. Considering this factor when identi-
fying traces of petroleum products modified under
these conditions, it is reasonable to determine the con-
tent of condensed alkylarenes in view of their relatively
high evaporation temperature and higher stability to
oxidation. Moreover, oxygen deficiency is often
observed under fire conditions, which also facilitates
retention of aromatic hydrocarbons.
High-performance liquid chromatography (HPLC)
with photometric detection in the UV spectral range is
most appropriate to analyze arenes of petroleum prod-
ucts. This method provides a sufficiently high molar
extinction coefficient for aromatic hydrocarbons. In
this case, preference is given to the normal-phase
HPLC version, since petroleum products contain alky-
larenes not eluated under conditions of the reversed-
phase version.
Arenes are identified in chromatograms not only by
the retention time but also by the distribution of absorp-
tion spectral lines at peak points. Monocyclic arenes
(benzene derivatives) are characterized by strong absorp-
tion in the wavelength range of 195–215 nm; for naphtha-
lene derivatives, a peak at 220–230 nm is characteristic;
for tricyclic derivatives, a peak at 250–260 nm is typical
[6, 7]. The presence of this set of aromatic hydrocarbons is
characteristic of petroleum nature substances.
An analysis of published data and the study per-
formed showed that fractions of condensed bicyclic
arenes of evaporated gasolines mainly contain methyl
and ethyl derivatives of naphthalene and acenaphthene
and polycyclic arenes, i.e., phenanthrene, anthracene,
their mono-, di-, and trisubstituted methyl and ethyl
isomers, fluorene and its isomers, fluoranthene, pyrene,
benzofluorene, etc. Among condensed tricyclic arenes,
alkyl derivatives of phenanthrene (mono- and dimethyl
derivatives) dominate in petroleum products. The stron-
gest peak in the chromatogram of evaporated automo-
bile gasoline corresponds to monomethyl derivatives of
condensed tricyclic arenes (Fig. 1). Petroleum products
are always characterized by no less than three strong
peaks of tricyclic arenes, while pyrolysis products of
wood, polymers, and other materials formed under fire
conditions yield one or two strong peaks of these com-
pounds. Moreover, the height of the second-large peak
in the multiplet of tricyclic arenes (dimethyl and
anthracene derivatives) is no less than 40% of the peak
of monomethyl derivatives. This value is significantly
smaller in chromatograms of pyrolysis products of car-
rier objects. This feature makes it possible to distin-
guish aromatic hydrocarbons corresponding to petro-
leum products from arenes formed under fire condi-
tions.
It should be noted that the anthracene peak almost
coincides with phenanthrene and pyrene peaks in reten-
tion time, monomethyl derivatives of anthracene merge
into a single peak and coincide with the peak of
monomethyl derivatives of phenanthrene, and so on
under HPLC conditions. Such overlap and summation
of peaks allows us to determine the total content of the
above compounds without individual identification. In
studying middle distillate petroleum products subjected
to free evaporation and burning, it was found that the
ratio of multiplet heights of tricyclic and bicyclic
hydrocarbons at λ = 254 nm (h3) and at λ = 230 or λ =
220 nm (h2), respectively, does not exceed 0.45 (for
chromatographic columns with thermally activated
SUasorb-600 sorbent). At the same time, this value can
be higher for gasolines for internal combustion engines
and their mixtures with middle distillate petroleum
products (see Figs. 1 and 2).
The dependences of the parameter h3/h2 on the
degree of evaporation expressed as the evaporated
region width were plotted for different petroleum prod-
ucts. The evaporated region width was denoted in plots
by the number of carbon atoms of n-alkane from which
the gas chromatogram of evaporated petroleum product
started.
The diesel fuel evaporation curve (Fig. 3a) contains
a maximum corresponding to k3/k2 = 0.40, which is several
tens of times smaller than the same parameter obtained for
evaporated gasolines for internal combustion engines
(automobile and aviation gasolines) (Fig. 3b). This is
because middle distillate petroleum products contain a
INORGANIC MATERIALS Vol. 45 No. 14 2009
 STUDY AND ANALYSIS OF GASOLINES MODIFIED 1595

significant amount of bicyclic arenes whose degree of

substitution and mass of aliphatic and naphthenic sub-
stituents are much larger than those of gasolines. The
degree of substitution with alkyl radicals and their mass 230 nm
have an insignificant effect on the retention time of are-
nes; in the study by the HPLC method (under the con-
ditions used), they are eluated by sequential groups [8].
However, the degree of substitution and substituent 220 nm
210 nm
mass significantly affect the boiling and evaporation
temperatures of aromatic hydrocarbons. The GZHH 254 nm
study showed that condensed tricyclic arenas of petro-
leum products evaporate sooner than monocyclic and
bicyclic aromatic hydrocarbons containing heavy
(long-chain) aliphatic and naphthenic substituents. The
presence of such substituted bicyclic arenes results in
that the parameter h3/h2 initially increases to a maxi- Fig. 2. Chromatogram of evaporated diesel fuel.
mum value during petroleum product evaporation and
then begins to decrease. When the evaporated region objects are arranged in the gas chromatogram against
width reaches n-docosane, differentiation of traces of the background of peaks of coextractive substances
modified petroleum products becomes impossible
which complicate identification of petroleum product
owing to disappearance of condensed tricyclic arenes.
components.
In general, carrier objects are removed from fire
regions, on which the degree of petroleum product Traces of gasoline for internal combustion engines
evaporation is already sufficient for differentiation. can also be determined in mixtures with lubricants.
However, it is often necessary to work with objects Two regions with boundaries 2.0–5.6 and 5.6–14.0 min
whose degree of evaporation did not reach a value at can be distinguished in the chromatogram of motor
which middle distillate petroleum product can be dis- mineral oil from an internal combustion engine crank-
tinguished from gasoline for internal combustion
engines; therefore, such samples require additional
evaporation, which results in a maximum value of 0.45 (a)
Relative peak height h3/h2

h3/h2. 0.40
The curves in Fig. 3 show that the parameter h3/h2 is 0.35
maximum when the evaporated region width reaches n- 0.30
octadecane. Therefore, if components to n-C18H38 are 0.25
absent in traces of petroleum product under study, these 0.20
objects do not need further evaporation with the pur- 0.15
pose of establishing the greatest possible parameter
0.10
value.
0.05
The relatively high content of condensed tricyclic
arenes in gasolines for internal combustion engines 0
2 4 6 8 10 12 14 16 18 20 22
allows determination of their traces in evaporated mix- Evaporated region width
tures with middle distillate petroleum products. In gen- (b)
Relative peak height h3/h2

eral, it is possible to determine traces of modified gas- 19.7

oline when its content in the initial mixture is no less
than 10–12%. In the case of an analysis of an evapo- 15.7
rated mixture of diesel fuel and automobile gasoline 11.7
initially taken in a ratio of 9 : 1, there are no features
allowing determination of gasoline traces, whereas the 7.7
parameter h3/h2 calculated by liquid chromatography
data (it exceeds 0.45) indicates the presence of modi- 3.7
fied gasoline for internal combustion engines in the
object of study. The gas chromatogram of automobile –0.3
gasoline modified by evaporation is also not so infor- 2 4 6 8 10 12 14 16 18 20 22
Evaporated region width
mative in comparison with its liquid chromatogram
(see Fig. 1). This becomes particularly evident if we Fig. 3. Dependence of the parameter h3/h2 on the degree of
consider that the (typically low-intensity) peaks corre- evaporation of (a) summer diesel fuel and (b) automobile
sponding to modified gasoline components in real gasoline.

INORGANIC MATERIALS Vol. 45 No. 14 2009

1596 TEMERDASHEV, KOLYCHEV
250 nm
220 nm
230 nm
254 nm
240 nm
Fig. 4. Chromatogram of engine mineral oil from an inter-
nal combustion engine crankcase.
case (Fig. 4). The first chromatogram region in its
retention times and distribution of spectral absorption
lines at peak points (spectral ratios) corresponds to
mineral oil. The second region represents two multip-
lets which, in its retention times, spectral ratios, and the
parameter h3/h2 = 1.08, correspond to gasoline for inter-
nal combustion engines.
To determine the cause of the high content of methyl
derivatives of condensed tricyclic arenes in gasolines
for internal combustion engines, all components of
automobile and aviation gasolines and raw materials
from which they were produced were studied. It was
found that studied gasolines are characterized by a rel-
atively high content of polyaromatic hydrocarbons due
to the presence of products of catalytic reforming and
catalytic cracking. In this case, the largest contribution
is made by catalytic reforming gasolines.
The detection and differentiation of traces of modi-
fied gasolines solvents and straight-run gasolines are
complicated, since they do not contain a sufficient
amount of polycyclic aromatic compounds. Traces of
such gasolines can be determined by the chromatogram
profile in the bicyclic arene region under the condition
that components of middle distillate petroleum prod-
ucts are absent (the absence of middle distillate petro-
leum products was confirmed by the GLC method). A
characteristic feature of modified gasolines, in contrast
to modified middle distillate petroleum products, is the
shape of the multiplet corresponding to bicyclic arenas.
These compounds contained in modified (evaporated)
middle distillate petroleum products are eluated in the
form of an extended peak with a rounded vertex and
weakly expressed profile inflections (see Fig. 2). The
sloping profile of chromatograms of evaporated middle
distillate petroleum products is caused by a large num-
ber of homologous series of hydrocarbons of a mixed
structure type, i.e., containing both aromatic and naph-
thenic rings and aliphatic substituents [9]. A comb-
shaped elution with multiple peaks at the vertex and
slopes is characteristic of bicyclic gasoline compounds
(see Fig. 1). Features of bicyclic arenes of gasolines are
lost in chromatograms of evaporated (burned) mixtures
of gasolines and middle distillate petroleum products.
The HPLC method in the normal-phase version on
thermally activated silica gel allows revealing diagnos-
tic features of petroleum products of different classes.
The parameter of the relative concentration of alkylare-
nes was experimentally obtained, which allows high-
reliability identification of traces of gasolines for inter-
nal combustion engines in afterfire residues and evapo-
rated mixtures with other petroleum products. This
technique makes it possible not only to detect and dif-
ferentiate petroleum product traces, but also to distin-
guish them from products of pyrolysis of carrier objects
formed under fire conditions. The capability of the pro-
posed method is much greater than those of existing
criminal investigation and ecoanalytical techniques for
establishing the fact of the presence of traces of gaso-
lines undergoing radical changes owing to evaporation
and burning in (on) objects of study.
The developed technique was implemented in the
practice of the Krasnodar Forensic Examination Labo-
ratory of the Ministry of Justice of the Russian Federa-
tion.
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