EFFECT OF THE ETHANOL CONTENT

ON THE EVAPORATION RATE OF BTEX

FROM GASOLINE
A. R. FINOTTI*, F. FEDRIZZI*, C. E. TEIXEIRA*, I. NASCIMENTO**
*

Environmental Sanitation Institute

Physics and Chemistry Department University of Caxias do Sul, Avenida
Francisco Getlio Vargas, 1130, Caxias do Sul, RS Brazil, CEP 95070-560

**

SUMMARY: The main objective of this work is to assess the influence of the intermolecular
forces on the evaporation rate of benzene, toluene, ethylbenzene and xylenes (BTEX) from
gasoline/ethanol mixtures. With this purpose, batch tests were performed with glass flasks
capped with rubber and aluminium rings containing pure gasoline and mixtures of
ethanol/gasoline, with 5, 10, 20, and 25% (v/v) of ethanol and the experimental time was of four
weeks. The instrumental analysis was performed by Gas Chromatography with a Flame
Ionization Detector. It was observed that the evaporation rate for all BTEX was positive only in
the ethanol concentration range between 5 and 10% (v/v) and that, probably, intermolecular
forces among the ethanol and BTEX molecules can exert a strong influence over the evaporation
rate of these late.
1. INTRODUCTION
After the first oil crisis in the 70s, with growing environmental pollution and the need for
clean energy production, several nations around the world developed programs to support the use
of alternative fuels, including ethanol and gasohol (which is an ethanol-gasoline blend) as
automobile fuels. The main advantages of the ethanol blend fuels are reduction of greenhouse
gas emissions and enhancement of the octane number of gasoline. The ethanol content in
Brazilian gasoline ranges from 24% to 26% (Brazil, Federal Law 8723,1993) and, despite the
mixture benefits, the presence of ethanol in gasoline can enhance the BTEX volatilization.
United States and othe conutries of the Europe start the replacement of fossil fuels by biomass
fuels, trying to reduce the harmful gases emissions. Ethanol is an alternative to the pure gasoline
and the study of their properties is very important to access the impact of its use to prevent
possible undesirable consequences. In this work we evaluate the impact on vaporization of the
must toxics components of gasoline.
Gasoline compounds may evaporate from spills of underground storage tanks or by
accidental releases and give rise to a vapor plume just above the contaminated soil, which can
also migrate. In this way, the soil contaminated with gasoline or gasoline/ethanol can be
considered as an hazardous waste. For any volatile compound, the rate of evaporation is a
function of temperature, wind-speed, atmospheric conditions, solar radiation, the oil spill
dimensions and the volatility and diffusion characteristics of the fuel (Mackay and Matsugu,

1973). The chemical composition of gasoline varies, but aliphatic compounds (4 to 12 carbon
atoms) are present in 60 to 90% and aromatic ones (6 to 8 carbon atoms) represent 10 to 40% per
volume. Compounds with 4 to 6 carbon atoms volatilize rapidly and BTEX are the chemicals of
greatest concern because of their toxicity and carcinogenic activity (Hsieh & al, 1999).
Furthermore, they are very mobile, volatile and are not well retained by organic matter in the
soil. In gasohol the BTEX physical and chemical properties undergo changes that may increase
the groundwater pollution. Some of these changes reported in the literature are variations of free
phase measurements in monitoring wells (Finotti & al, 2005, Finotti & al, 2006) co-solvency
effects that render BTEX solubility higher in the presence of ethanol (Courseuil & al, 2004),
preferable biodegradation of ethanol in gasohol plumes, which causes anoxic conditions for
BTEX degradation (Courseuil and Alvarez, 1996, Courseuil et. al., 1996) and effects of gasohol
contamination (Courseuil & al, 1997, Powers & al, 2000, Powers & al, 2001, Montgomery and
Welkom, 1989). Other studies are focused on the thermodynamic properties of ethanol and
gasoline-blended fuel, behavior of entrapped petroleum products in the subsurface, and soil
vapor extractions systems (Nan and Tan, 2005, Dror & al, 2001, Yang & al, 2001) or
measurements of the vapor pressure enhancement of alcohol-gasoline blends (Pumphrey & al,
2000).
However, despite the well-known harmful effects of BTEX on humans and the environment,
information about which individual BTEX have their volatilization grade increased by the
addition of ethanol and what range of ethanol concentration in gasohol increases or decreases
this volatilization is still lacking in the literature.
The main objective of this wok was to analyze the influence of ethanol on the evaporation
rate of each individual BTEX, compared to pure gasoline. For this purpose batch tests (serum
bottles) with vapor collection of pure gasoline and mixtures of ethanol/gasoline (5, 10, 20, and
25% of ethanol (v/v)) were performed. The BTEX volatilization was analyzed by Gas
Chromatography with a Flame Ionization Detector (GC/FID). The percent areas of BTEX were
calculated by the internal normalization method.
2. EXPERIMENTAL SECTION
2.1 Samples and solvents
The pure gasoline samples were kindly provided by Laboratrio de Motores, REFAP PETROBRAS. All reagents and solvents used in this work were of PA grade.
2.2 Monitoring the effect of the ethanol content on the BTEX evaporation grade
Tests to quantify the variation of the BTEX concentrations in headspace flasks for pure
gasoline and different gasoline/ethanol blends (5, 10, 20 and 25% of ethanol) were performed in
35 mL serum bottles. The total samples volume was 20 mL. The serum bottles were closed with
a rubber cap and aluminum ring and left at room temperature overnight. After this, four 5 L
injections of the vapor phase of all the flasks were made into the gas chromatograph and the peak
areas of the BTEX were evaluated.
2.3 Monitoring the time effect on the BTEX evaporation grade
Two flasks (identical to those cited above) were used in this experiment. The first was filled
with 20 mL of gasoline/ethanol (20% ethanol (v/v)) mixture. The second was filled with the
same volume of pure gasoline. Both flasks were closed with a rubber cap and aluminum ring
and left at room temperature.

After one week, the first analysis was performed by four injections of 5 L of the flasks
headspace into the gas chromatograph. These procedures were repeated for the next 3 weeks..
The chromatograph availability was the reason for the one week interval between each extraction
and chromatographic analysis.
2.4 Instrumental analysis
The instrumental analysis was performed in an AutosystemXL gas chromatograph (Perkin
Elmer) with Flame Ionization Detection (FID). The samples were injected in the splitless mode.
A 30 m Elite column (film thickness 0.25 m, internal diameter 0.25 mm) was temperatureprogrammed from 40 C (held for 10 min) to 220 C (held for 0 min) at 5 C/min. Helium was
the carrier gas and the carrier gas flux was 1mL/min. The detection limits (determinated by an
aqueous standard solution of BTEX and ethanol) were of 0.4 mg L-1 for benzene, toluene and
ethylbenzene and 0.3 mg L1 for xylenes.

3. RESULTS AND DISCUSSION

The effect of ethanol content on the percentual area of BTEX is presented in Figure 1 (values
with the respectives standard deviations can be seen in Table 1). With exception of xylenes, the
maximum BTEX volatilization occur at an ethanol content of 10 % (v/v/). These results are in
agreement with the elevation of gasoline vapor pressure observed by Pumphrey et al (2000).
According to those authors, the vapor pressure of the gasoline was initially elevated by the
addition of ethanol and then lowered as the proportion of alcohol was increased.

Figure 1. Effect of the ethanol content on the average percent area of the chromatographic peaks
of BTEX.

Table 1. Average percent areaa (SD) of the chromatographic peaks of BTEX as a function of
the ethanol content.
Compound
0%
Benzene
0.41 (0.08)
Toulene
0.15 ( 0.01)
Ethylbenzene
0.02 ( 0.01)
xylenes
0.01 ( 0.01)
a
Trplicate of injection
a
Not detected

Ethanol content
5%
10%
20%
0.22 (0.05) 0.33 (0.01) 0.29 (0.01)
0.05 (0.02) 0.12 (0.01)
0.10 (0.05)
0.01 (0.01) 0.04 (0.01)
0.04 (0.02)
ND
ND
NDa

25%
0.26 (0.01)
0.08 (0.03)
0.04 (0.01)
ND

Heermann and Powers (1998) and Finotti & al (2005) assumed that ethanol affects BTEX
volatilization by altering the compounds proportions and the surface and interfacial tension,
compared with pure gasoline but, despite the remarkable contribution of those works, no
explanation was provided about how each individual BTEX in gasoline is affected by the ethanol
content. From this point we will try to explain it on the basis of the intermolecular forces theory.
Between zero and 5% (v/v) of ethanol, the percentual area of all BTEX decreases, suggesting
that at this point interactions like hydrogen bonds among the alcohol molecules are too strong to
allow the complete diffusion of ethanol in the gasoline (that is less polar than ethanol). Thus, the
density of the ethanol phase is higher than the gasoline phase. If, in this situation, the net density
is increased, the volatilization of BTEX is lowered (Table 1, first and second columns).
Between 5 and 10% (v/v) of ethanol, the percent area of all BTEX increase, suggesting a
higher diffusion of the ethanol molecules (probably because the increase of the repulsion forces)
and a decrease of the solution density that favors the BTEX volatilization.
At ethanol concentrations higher than 10% (v/v) all BTEX volatilizations decrease. This
result suggests that in this range of concentration, the ethanol, that have the lowest boiling point,
compared with BETEX (Lide, 1996), occupy most of the headspace volume and dificults the
volatilization of the other compounds. This explanation is supported by the decrease of the
volatilization rate of BTEX after the second week (Table 2).
Table 2. Volatilization ratio of BTEX in pure gasoline and gasoline/ethanol samples.

Compound
Benzene
Toulene
Ethylbenzene
xylenes

Compound
Benzene
Toulene
Ethylbenzene
xylenes
a

Tiplicate of injection

Week #1
66.76 (14.17)
24.10 ( 0.35)
30.98 ( 8.54)
14.89 ( 6.11)

Week #1
70.58 (23.58)
20.51 (0.12)
26.83 (5.47)
16.23 (3.93)

Pure Gasoline
Average peak areaa (area units) SD
Week #2
Week #3
Week #4
101.02 (80.50)
0.15 (0.11)
2.78 (1.60)
96.15 (45.43)
10.23 (1.90)
26.76 (24.03)
12.65 (8.51)
6.14 (0.07)
35.02 (26.64)
8.29 (2.13)
9.98 (1.46)
16.77 (3.70)
Gasoline/ethanol
Average peak areaa (area units) SD
Week #2
Week #3
Week #4
27.43 (29.80)
7.49 (0.61)
3.48 (3.01)
266.29 (177.78)
70.09 (28.02) 38.77 (16.15)
7.49 (2.35)
29.85 (2.46)
7.48 (5.84)
7.66 (3.44)
11.61 (4.92)
3.13 (1.23)

4. CONCLUSIONS
Considering the growing interest in alternative fuels worldwide, and especially in
ethanol/gasoline blends, it is important to take into account whether BTEX will have their
volatility increased or decreased, according to the ethanol content. Benzene and toluene are wellknow toxic compounds and at ethanol contents ranging from 5% to higher than 10% (v/v), Their
volatilization are drastically favored. This is an worrying fact to be considered in the handling
and storage of gasoline/ethanol blends to avoid human exposure and environmental damages.
Obviously these are preliminary results and a set of new experiments regarding a larger sampling
time and mass balance calculations of gasoline and gasoline/ethanol mixtures must to be
performed for a better knowledge of the entire picture of BTEX volatilization from the gasohol.
ACKNOWLEDGMENTS
The authors thank to PRONEX FAPERGS and CNPq for the financial support and
PETROBRAS, Alberto Pasqualini Refinery, Laboratrio de Motores.

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