Fuel 86 (2007) 323–327

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Molar enthalpy of vaporization of ethanol–gasoline

mixtures and their colloid state
Roman M. Balabin *, Rustem Z. Syunyaev, Sergey A. Karpov
Gubkin Russian State University of Oil and Gas, 119991 Moscow, Russian Federation

Received 15 June 2006; received in revised form 4 August 2006; accepted 8 August 2006
Available online 8 September 2006

Abstract

Vapour pressure measurements are used to evaluate the enthalpy of vaporization of ethanol–gasoline mixtures. Partial molar values are
also derived. The dispersed structure of ethanol–gasoline fuel is studied for the first time using the method of correlation spectroscopy of
scattered light. A large range of dispersed particle sizes in different alcohol–gasoline systems is found. The dependence of the mean radius
of drops on ethanol content is determined. It is found that coalescence phenomenon occurs in the systems when extra ethanol is added.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Ethanol–gasoline fuel; Enthalpy of vaporization; Dispersed structure

1. Introduction or alcohols), and water, at approximately ambient temper-

Nations today often face divergent challenges in the form
of climate change, air pollution, energy production, con-
sumption security, and shrinking oil supplies. In response
to these challenges, countries around the world have
developed programs to support the use of clean fuels,
including ethanol [1,2].
The properties of gasoline have been altered in recent
years to reduce motor vehicle emissions of carbon monox-
ide, photochemical smog precursors, and toxic organic air
pollutants such as benzene. Changes have been made to
sulphur, olefin, and aromatic contents, and to distillation
properties of gasoline.
Presently, there is an increasing interest in adding oxy-
genated compounds to gasoline, because of their octane-
enhancing and pollution-reducing capabilities. In the last
several years, many interesting works on ternary, quater-
nary, or quinary systems that contain a synthetic reformate
(hydrocarbon mixtures), an oxygenated compound (ethers
*
Corresponding author. Tel.: +7 926 592 7920; fax: +7 495 335 8639.
E-mail address: balabin.r@gubkin.ru (R.M. Balabin).
atures, have been published [3–19]. However, studies of
systems that contain gasoline, an oxygenated compound,
and water are not often found in the literature [20].
Among the oxygenated compounds, ethers and alcohols
are the most important. Currently, among ethers and alco-
hols, ethanol has been receiving more attention [21,22].
Controversy has surrounded another major fuel change:
the addition of methyl tert-butyl ether (MTBE) [23,24].
Presently, there is no requirement that a specific oxygenate
be added to gasoline. However, the use of MTBE in gaso-
line was phased out in California at the end of 2002 due in
part to concerns about surface water and groundwater con-
tamination. Likewise, the United States Environment Pro-
tection Agency (USEPA) intends to significantly reduce the
use of MTBE in gasoline nationwide [25]. These decisions
will lead to greater dependence on ethanol–gasoline blends
and gasoline formulations that do not contain oxygenated
compounds.
One of the major difficulties encountered in the use of
alcohol–gasoline blends is their tendency to phase-separate
on contact with small amounts of water.
Vapour pressure is one of the most important physical
properties of gasoline mixtures because it defines the

0016-2361/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2006.08.008
324 R.M. Balabin et al. / Fuel 86 (2007) 323–327
volatility of the mixtures. Vapour pressure can be deter-
mined by a variety of methods that are rather time-con-
suming. The refinery industry utilizes the Reid methods
[26] to determine vapour pressure, which is related to the
gasoline performance characteristics and to its storage
behaviour [27].
Evaporative emissions occur by a wide variety of mech-
anisms, including fuel spillage and vapour displacement
during refuelling, venting of fuel tank vapours as ambient
temperature changes, fuel evaporation from the engine
compartment of parked vehicles due to residual engine
heat, liquid leaks in vehicle fuel systems, and so on [28].
There is concern about increased evaporative emissions
of volatile organic compounds (VOCs) when ethanol is
blended with gasoline, because such blends tend to have
higher Reid vapour pressure (RVP) than equivalent
MTBE-blended fuel [24].
The thermodynamic properties of ethanol–gasoline mix-
tures have not been widely covered in the literature (with
the exception of heat capacity [1,29,30]), but these proper-
ties are necessary as they serve as basic thermodynamic
data for the investigation of clean fuels. Enthalpy of vapor-
ization is the most important thermodynamic constant that
describes liquid–gas equilibrium.
The polarity of ethanol and nonpolarity of gasoline
hydrocarbons are the reasons for the possible colloid state
of ethanol–gasoline mixture. Particle size (the main param-
eter of any colloid system) was never reported for ethanol-
containing fuel.
In this paper, vapour pressure measurements of pure
gasoline and its mixtures at three different temperatures
(20, 40, and 60 °C) using a MINIVAP VPS Vapour Pres-
sure Tester are presented. Enthalpy of vaporization is cal-
culated using the Clausius–Clapeyron equation. Partial
molar enthalpy of vaporization of ethanol and gasoline is
also evaluated.
The colloid state of ethanol–gasoline mixtures is also
examined by scattered light correlation spectroscopy.
2. Experimental section
2.1. Materials
Table 1 lists the properties of two typical unleaded
gasoline (supplied by Yukos Oil Company), called A and
Table 1
Parameters of gasoline used in this paper
Parameter Units Value
Gasoline A
Motor octane number (MON) – 83.0
Research octane number (RON) – 92.0
Density at 20 °C kg/m3 750
Actual gums mg/100 cm3 4.8
Sulphur content wt% 0.05
Benzene content vol% 5.1
Water content in added ethanol vol% 4.0
B, used in the experiments. Two types of ethanol with
different water content – 4 vol% in line A (with gasoline
A) and <0.5 vol% in line B (with gasoline B) – were
used.
Alcohol–gasoline mixtures were prepared in confor-
mance with standard procedures without any special equip-
ment.
Line A: 0, 1, 2, 3, 4, 5, and 10 vol% of ethanol in gaso-
line A.
Line B: 0, 2, 4, 6, 8, and 10 vol% of ethanol in gasoline
B.
Samples of line A (with 4% of water in ethanol) showed
instability and phase-separation tendency. Samples of line
B were stable. It confirms that water content in the alco-
hol–gasoline mixture is the most important parameter that
defines system phase stability.
2.2. Methods
All measurements of vapour pressure were performed
using a MINIVAP VPS vapour pressure tester (GRAB-
NER INSTRUMENTS GmbH). This instrument is used
to determine the vapour pressure of low-viscosity petro-
leum products. Tests can be carried out at temperatures
ranging from 20 °C to 60 °C and at a vapour-to-liquid ratio
of 4:1, with the condition that the resulting pressures do
not exceed 1000 kPa. The accuracy of the temperature
readings is 0.1 °C. Repeatability of vapour pressure mea-
surements was 0.5 kPa, reproducibility – 1.6 kPa.
The vacuum in MINIVAP VPS is achieved by a pump
that is capable of achieving and maintaining a pressure
of better than 0.1 kPa. The vapour-to-liquid ratio is deter-
mined by the volume of the sample used.
All the samples were prepared in strict conformance
with the requirements of ASTM D-5191. In all measure-
ments performed in this study, the corresponding val-
ues were always within the range recommended by the
manufacturer.
The study of the sizes of scattered objects in alcohol–
gasoline mixtures was made using the method of correla-
tion spectroscopy of scattered light. He–Ne laser was used
as a radiation source. The beam of the light scattered by
the sample (angle of scattering was 90°) was divided after
diaphragm into two beams, which were directed to the
two photoelectronic multipliers HAMAMATSU R6358P,
working in the photon count regime. The signals formed
by the multipliers were intensified by the same amplifiers.
Gasoline B
The signals from the amplifiers were directed to the loga-
rithmic 32-bit correlator PHOTOCOR-FC, measuring the
76.0
80.0
correlation function in the real-time scale. The obtained
725 correlation function was equivalent to the correlation func-
4.9 tion of the light, scattered by the sample, because photo-
0.05 electronic multipliers registered the light from the same
2.5 scattered volume and the noises of the two multipliers were
<0.5
not correlated.
 R.M. Balabin et al. / Fuel 86 (2007) 323–327 325

It is known that for monodisperse scattering objects in gasoline mixtures were not expected to approach ideal
solution: behaviour (so Raoult’s law cannot be used). This result
was repeatedly reported in both experimental and theoret-
C ¼ Dq2 ð1Þ
ical works but theoretical background of this phenomenon
where C is the diffusion expansion, characterizing the width needs further exploration. The behaviour of this kind can
of scattered light spectral contour; D is the diffusion coeffi- regard to azeotrope [32] or can be explained as exceed ther-
cient; q is the vector of scattering, which is given by modynamic property (by activity coefficients) [27,28,33].
We should note that structure of hydrocarbons forming
n h
q ¼ 4p sin ð2Þ azeotrope with ethanol in alcohol–gasoline mixture is still
k 2 unknown.
where h is the angle of scattering, k is the radiation length,
n is the refraction index of the environment. 3.2. Enthalpy of vaporization
The hydrodynamic radius R of spherical scattering par-
ticles is determined from the Stokes–Einstein relation: The enthalpy of vaporization was calculated using the
kBT well-known Clausius–Clapeyron equation for the evapora-
D¼ ð3Þ tion process:
6pg  R
where g is the viscosity of the environment, T is the temper- d ln p DH vap
¼ ð5Þ
ature, kB is Boltzmann’s constant. dT RT 2
If particles are polydispersed, R is a hydrodynamic where p is the vapour pressure at the temperature T; DHvap
radius corresponding to an average of the type [31] is the enthalpy of vaporization (supposed to be constant).
P 6
R The plot of the logarithm of ethanol–gasoline mixture
R ¼ Pi i5 ð4Þ vapour pressure versus inverse thermodynamic tempera-
i Ri
ture is presented in Fig. 2. Sufficient coincidence with Eq.
(5) is shown so enthalpy of vaporization can be assumed
3. Results and discussion temperature independent.
From the fitted linear expression, enthalpy of vaporiza-
3.1. Vapour pressure tion was evaluated for all samples in both lines.

Measured vapour pressure is presented in Fig. 1 for each
of the ethanol-containing gasoline samples (line A and B).
Both the graphs are extremal curves. The maximum of
vapour pressure is near 4 vol% for line A and 3 vol% for
line B.
This result shows the nonlinear behaviour of polar eth-
anol in nonpolar gasoline hydrocarbons mixture. Ethanol–
3.3. Partial molar enthalpy of vaporization
Fig. 3 shows the enthalpy of vaporization DHvap versus
the molar ethanol part in alcohol–gasoline mixture. To
evaluate molar values, the molar weight of gasoline was
assumed to be 100 g/mol; thus, all the obtained numbers
are approximate.

Fig. 1. Vapour pressure of ethanol–gasoline mixture samples of both lines Fig. 2. Dependence of vapour pressure logarithm on temperature for
(A and B) at 20 °C. samples 2 vol% (line A) and 2 vol% (line B).
326 R.M. Balabin et al. / Fuel 86 (2007) 323–327
Fig. 3. Enthalpy of vaporization of ethanol–gasoline mixture versus
ethanol concentration.
It is evident that the enthalpy of vaporization is a linear
function of the ethanol (or gasoline) molar part; hence,
partial molar values are constant. The values of DHvap for
both lines were fitted to the linear expressions by the
least-squares method. The results are
ðDH gas
vap ÞA  37:3 kJ=mol
ðDH eth
vap ÞA  45:9 kJ=mol
ðDH gas
vap ÞB  35:4 kJ=mol
ðDH eth
vap ÞB  47:9 kJ=mol
where DH vap is the partial molar enthalpy of vaporization.
The values of partial molar enthalpy of vaporization of
ethanol obtained in ethanol–gasoline fuel are close to the
values of ethanol DHvap reported in the literature (25 °C,
101.325 kPa): 42.3 kJ/mol [34].
3.4. Particle size
The study of sizes of the scattering objects in line B was
made using the method of correlation spectroscopy of scat-
tered light.
The intensity of the signal from microdrops of alcohol
(plus water) is low because of the little difference in the
refraction index of gasoline hydrocarbons and ethanol.
This leads to the great fallibility of defined colloid particles’
sizes (Fig. 4). However, it does not make any real sense
because the main idea of this part of the paper is the fact
that ethanol–gasoline mixtures consist of a dispersed phase
and a dispersion medium.
The colloidal structures are assumed to be microspheres,
although other structures are possible.
It is obvious that the size of the drops grows more
quickly (R / x3) than expected when the number of parti-
cles is constant (R / x1/3). We suppose that coalescence
occurs in the system when ethanol is added but other expla-
Fig. 4. Mean radius of dispersed particles (alcohol–water drops) in
ethanol–gasoline mixture (line B) at 22 °C.
nations are possible. We expect that our future works will
give us exact answer.
4. Conclusions
One of the most important thermodynamic properties of
ethanol–gasoline system – enthalpy of vaporization – was
studied. Values of partial molar enthalpy of vaporization
were reported for the first time. They are found to be con-
stant. These values can help normalize alcohol–gasoline
blended fuel volatility and make this fuel more competitive
than ordinary gasoline.
The dispersed structure of ethanol–gasoline mixture was
shown. The most important parameter of any colloid struc-
ture, i.e., the radius of the dispersed particles, was reported.
Its value is hundreds of nanometres and it dramatically
depends on the concentration of ethanol. These data can
help prevent phase-separation in ethanol–gasoline fuel
caused mainly by the coalescence of alcohol–water drops
and precipitation.
Changing the colloid structure of ethanol–gasoline sys-
tems can be an effective way to put in order the quality
coefficients of the fuel.
Acknowledgements
Balabin Roman is grateful to ITERA International
Group of companies for a nominal scholarship. The authors
acknowledge the Yukos Oil Company for supplying gaso-
line and the corresponding data.
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