Fuel 85 (2006) 1494–1497

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Quality analysis of automotive fuel using solvatochromic probes

Robert Budag, Luciano Albino Giusti, Vanderlei Gageiro Machado *, Clodoaldo Machado *
Departamento de Quı́mica, Universidade Regional de Blumenau, FURB, CP 1507, Blumenau, SC, 89010-971, Brazil
Received 7 May 2005; received in revised form 16 December 2005; accepted 23 December 2005
Available online 2 February 2006

Abstract
The effect of ethanol addition to pure gasoline on the solvatochromic band of dyes 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl)phenolate
(1), 2,6-di(4-tert-butylphenyl)-4-[2,4,6-tri(4-tert-butylphenyl)pyridinium-1-yl]phenolate (2), 1-(4-dimethylaminophenyl)-2-nitroethylene (3),
and 1-(4-dimethylaminophenyl)-2-nitropropene (4) was investigated. The dyes are very soluble in gasoline–ethanol mixtures. The data show the
occurrence of strong preferential solvation of the dyes by ethanol in all mixtures. Solutions of dye 2 are blue–green in gasoline, violet in ethanol,
and green–blue in gasoline with 25% of ethanol, which allows a naked-eye detection of the presence of ethanol in gasoline. Also, the use of
solvatochromic dyes to develop an analytical method for the determination of the quality of fuels is discussed.
q 2006 Elsevier Ltd. All rights reserved.

Keywords: Solvatochromic dyes; Gasoline quality; Naked-eye detection

1. Introduction Common procedures to analyze the quality of fuels involve

In Brazil, the past decade has been marked by much concern
regarding the quality of automotive fuels. The light-duty cars
of the Brazilian vehicular fleet are propelled by a mixture of
gasoline with 25G1% (v/v) of anhydrous ethanol, called
gasoline C, or with ethanol [1]. The end of the monopoly in
gasoline distribution and production has opened up a means for
its adulteration through the addition of illicit organic solvents
in gasoline. The more frequent adulterations involve the
addition of ethanol in excess and of hydrocarbons such as
kerosene, diesel, toluene, xylenes, hexane, and naphtha to
gasoline. Also, the addition of water in excess to ethanol is
common. The addition of solvents with a lower price than
automotive fuel has become a common procedure to improve
profits in this market [1,2]. The adulteration of the fuels
diminishes the lifetime of the engines because the fuels then
cause rubber corrosion, wear, vapor lock, problems with
starting, and increased knocking [2]. Furthermore, this practice
leads to environmental hazards [3–5] and is often associated
with tax evasion [1,2]. Therefore, endeavors have been
concentrated on the development of analytical methodologies
aiming to control automotive fuel quality [2,6–9].
* Corresponding authors. Tel.: C55 47 221 6081; fax: C55 47 221 6001.
E-mail addresses: gageiro@furb.br (V.G. Machado), clodo@furb.br
(C. Machado).
0016-2361/$ - see front matter q 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2005.12.023
mainly physical measurements, such as density, color, electric
conductivity, pH, flash point, and distillation. Since the
addition of solvents as adulterants may modify the physico-
chemical characteristics of the fuels, new analytical methods
need to be developed to monitor these alterations. One
approach to this is related to the fact that the addition of a
solvent to ethanol or gasoline may affect the polarity of the
medium, a general term that reflects the overall solvating
capability of the solvent [10,11]. Investigations into solvent
polarity are commonly performed with the use of solvato-
chromic probes [10–12]. These compounds undergo alterations
in the position of their charge-transfer bands in the UV–vis or
fluorescence spectra if the polarity of the medium is changed
[10–12]. Solvatochromic dyes have been extensively employed
in recent years in several studies related to solvatochromism
[10,12], halochromism [10,13–18], mixed solvents [10,11,19–
25], microheterogeneity in solution [26–28], and also in kinetic
studies [29–31]. Langhals proposed a procedure that allows the
use of the Reichardt’s betaine, 2,6-diphenyl-4-(2,4,6-tri-
phenylpyridinium-1-yl)phenolate (1), as a solvatochromic
probe for the determination of the water content in organic
solvents [32]. Thus, in principle, solvatochromic dyes could be
used as probes in the qualitative and quantitative determination
of contaminants in gasoline or ethanol. Qualitatively, the
presence of a particular contaminant would be detected by a
color change of the probe and, quantitatively, the extent of the
solvatochromic shift would be related to the amount of the
contaminant present in the fuel. In this paper, the effect of
 R. Budag et al. / Fuel 85 (2006) 1494–1497 1495

ethanol addition to pure gasoline on the solvatochromic band

of dyes 1, 2,6-di(4-tert-butylphenyl)-4-[2,4,6-tri(4-tert-butyl-
phenyl)pyridinium-1-yl]phenolate (2), 1-(4-dimethylamino-
phenyl)-2-nitroethylene (3), and 1-(4-dimethylaminophenyl)-
2-nitropropene (4) is investigated. Also, the use of
solvatochromic dyes in the development of a method for the
determination of the quality of fuels is discussed.

Fig. 1. Variations in the molar transition energies of the solvatochromic band of

dyes 1 (&) and 2 (†) in gasoline–ethanol mixtures.

mixtures. Compounds 2–4 are very soluble in gasoline and in

2. Experimental
2.1. Materials
Samples of gasoline and anhydrous ethanol were obtained
from PETROBRAS. Their analysis did not reveal the presence
of water or ethanol in gasoline samples. All other solvents were
HPLC grade and were purified following a methodology
described in the literature [33]. The following dyes were
synthesized and purified according to procedures described in
the literature: 1 [34], 3 [35,36], and 4 [35,36]. A sample of dye
2 [37] was kindly provided by Professor C. Reichardt.
2.2. UV–vis spectra of the dyes in the mixed solvents
UV–vis measurements were performed with a Shimadzu
UV-1601PC spectrophotometer at 25 8C, using a 1 cm quartz
square cuvette. The maxima on the UV–vis spectra (lmax) were
calculated from the first derivative of the absorption spectrum.
The l max values in nanometers, thus obtained, were
transformed into ET(dye) values, given in kilocalories per mole
according to the expression ET(dye)Z28,590/lmax.
A general procedure was used to take spectral measure-
ments of the dye solutions. Two 1.0!10K5 mol dmK3 stock
solutions of the dye were prepared in gasoline and in ethanol.
The gasoline–ethanol mixtures (v/v) were then prepared in
10 cm3 volumetric flasks and the spectrophotometric readings
were performed.
its mixtures with ethanol while dye 1, although not soluble in
gasoline, exhibits a good solubility in its mixtures containing
5% of ethanol. Plots of the ET values of each dye as a function
of the percentage of ethanol added are shown in Figs. 1 and 2.
A treatment of the data using preferential solvation models
based on solvent-exchange equilibria [20,22–25] could not be
performed since the mole fraction of gasoline could not be
calculated with precision (commercialized gasolines are
a complex mixture of hydrocarbons with variable compo-
sition). Therefore, the experimental data for each mixture
were simply fitted through a non-linear least-squares
procedure to a sixth-order polynomial of the form
ET ðdyeÞZ aC bXC cX 2 C dX 3 C eX 4 C fX 5 C gX 6 , where X
is the ethanol percentage in the mixture. Values for the
coefficients a, b, c, d, e, f, and g are displayed in Table 1 and
very good fits were obtained for all binary mixtures studied. In
addition, the calculated ET(dye) values for gasoline in Table 1
agree well with the experimental values.
Fig. 1 depicts the solvatochromic behavior of pyridinio-
phenolates 1 and 2 in gasoline–ethanol mixtures.

3. Results and discussion

The determination of the percentage of ethanol in gasoline

can, in principle, be easily carried out by the use of Fig. 2. Variations in the molar transition energies of the solvatochromic band of
solvatochromic probes if these compounds are soluble in the dyes 3 (†) and 4 (&) in gasoline–ethanol mixtures.
1496 R. Budag et al. / Fuel 85 (2006) 1494–1497
Table 1
Values of the coefficients a, b, c, d, e, f and g in the polynomial ET ðdyeÞZ aC bXC cX 2 C dX 3 C eX 4 C fX 5 C gX 6 for dyes 1–4 in gasoline–ethanol mixtures
Dye Coefficients
a b c d
1 45.53 0.178 K4.77!10 K3
8.97!10
2 42.95 0.403 K1.72!10K2 4.14!10K4
3 71.06 K0.0999 K1.77!10K3 1.16!10K4
4 73.03 K0.183 7.85!10K3 K2.44!10K4
All r2 values O0.998.
The solvatochromic band of compound 1 registers a
hypsochromic shift from 617.0 nm in a mixture containing
5% of alcohol to 560.0 nm in ethanol, corresponding to a shift
of 57 nm. Compound 2 exhibits a very important solvato-
chromic effect, with a shift from 666.2 nm in gasoline to
568.0 nm in ethanol, corresponding to a hypsochromic shift of
98.2 nm. Also, the data in Fig. 1 show the occurrence of strong
preferential solvation (PS) of the dyes by ethanol in all
mixtures. This phenomenon occurs when the solute has in its
microenvironment more of one solvent than the other, in
comparison to the bulk composition [10,19–25]. It has been
reported that the pyridiniophenolate 1, the basis for the ETN
polarity scale, is able to interact through hydrogen bonding
with proton donors by means of its phenolate group [38–40].
The possibility for hydrogen bonding leads to the stabilization
of the ground state of the dye, and a consequent increase in its
charge-transfer transition energy. Thus, the greater the
capability of the solvent to form hydrogen bonds with the
dye the greater the increase in the ET(dye) values. The PS of 1
and 2 by the more polar component can be explained based on
these dye–ethanol specific interactions [22,23].
The solvatochromic behavior of dyes 3 and 4 in gasoline–
ethanol mixtures is shown in Fig. 2. Bathochromic shifts in the
solvatochromic band of the dyes are observed if these dyes are
transferred from gasoline (402 nm for dye 3 and 391 nm for
dye 4) to ethanol (430 nm for dye 3 and 417 nm for dye 4).
Also, the plots in Fig. 2 show that the dyes are preferentially
solvated by ethanol in all mixtures, a behavior similar to that
observed with the pyridiniophenolates 1 and 2. Thus, it seems
reasonable that specific interactions through hydrogen bonding
between the hydroxylic group in the alcohol and the
dimethylamino group in the donor moiety of the dyes are
responsible for the observed behavior.
Some studies were performed in order to investigate the ability
of the solvatochromic dyes to probe the polarity of the gasoline
with petroleum ether or benzene as contaminants. These solvents
have similar polarities to those used in the adulteration of
gasoline. The dyes revealed a poor ability to indicate changes in
the polarity with the addition of 2% of petroleum ether or
benzene. This limit was used because the adulteration of gasoline
with this kind of solvent does not surpass this percentage. For
instance, it was observed that the addition of 2% of petroleum
ether or benzene to gasoline containing 2 provokes a bath-
ochromic shift of only 3.3 nm. These data are of interest because
they show that the dyes are very selective as probes to indicate the
presence of ethanol in gasoline. Furthermore, since the presence
e f g sd
K5
K9.42!10 K7
5.09!10 K9
K1.09!10 K11
6.6!10K2
K5.29!10K6 3.42!10K8 K8.85!10K11 6.5!10K2
K2.06!10K6 1.57!10K8 K4.33!10K11 6.2!10K2
4.03!10K6 K3.25!10K8 1.02!10K10 7.3!10K2
of water increases the polarity of these mixtures, these probes are
also able to indicate the presence of water in gasoline, other
contaminant commonly used in the adulteration of gasoline–
ethanol mixtures.
4. Conclusions
Dyes 1–4 were successful as polarity probes in gasoline–
ethanol mixtures, and were thus capable of quickly quantifying
amounts of ethanol in gasoline samples. The solvatochromic
band of dye 2 in ethanol is hypsochromically shifted by
98.2 nm in relation to gasoline, while dyes 3 and 4 exhibit
bathochromic displacements of 28.0 and 26.0 nm, respectively.
In the case of pyridiniophenolate 2, solutions show a blue–
green color in gasoline and are violet in ethanol, passing
through a green–blue color in gasoline with 25% of ethanol.
This means that this dye may be used for naked-eye detection
of ethanol in gasoline.
An important requirement for the use of a solvatochromic
dye in this method of analysis is that it must have hydrophobic
properties in order to be soluble in non polar media. It is also
important to study new classes of hydrophobic probes, with
easy synthesis and displaying large color alterations, to
determine their ability to indicate and quantify selectively
other common types of adulteration in gasoline. Another
related strategy would be the study of chromo- and
fluororeactands [41,42] as indicators for the detection of
neutral analytes present in the fuels. These studies would be of
great interest for the development of simple methods leading to
the quick automotive fuel analysis.
Acknowledgements
The financial support of Brazilian Conselho Nacional de
Pesquisa Cientı́fica e Tecnológica (CNPq), CTPETRO,
PETROBRAS and FURB is gratefully acknowledged.
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