Documente Academic
Documente Profesional
Documente Cultură
Pearson et al.
be viewed as a mechanism to incentivise the FFV customer to use E85, the proposition is only reasonable if
there are a sufficient number of fuel stations offering
the fuel.
In contrast with the CAFE regulations which make
it attractive to manufacture FFVs in the USA, the fiscal
penalties for GHG emissions from cars sold in the EU
is based on only tailpipe carbon dioxide (CO2) emissions. This gives vehicle manufacturers no incentive to
spend even the small extra amount required in order to
produce an FFV (about e100 per vehicle). It has been
suggested11 that attributing some CO2 benefit to manufacturers will provide a compelling reason for original
equipment manufacturers (OEMs) to make FFVs and
thus to produce a greater outlet for ethanol as an automotive fuel. The EU vehicle tailpipe CO2 penalty system does, however, at present allow a 5% reduction in
the tailpipe CO2 emissions to be claimed for any FFV
that an OEM sells, provided that the one third of the
fuel stations in the country in which the vehicle is sold
has at least one E85 pump. 13 Furthermore, for a vehicle emitting the 2011 EU average of 135.7 (g CO2)/km,
and at the highest proposed fine rate in 2015 of e95 per
(g CO2)/km, this represents a saving to the manufacturer of e541 per car (with the benefit limited to 5.7 (g
CO2)/km in this instance since the target would be
achieved), which the present authors contend is significantly greater than the additional costs of producing a
flexible-fuel-capable E85 vehicle.14
The use of an additional lower-cost blend component which is miscible with gasoline may provide an
opportunity to supply higher levels of ethanol in fuels
for FFVs which remain cost competitive for the consumer in terms of the distance travelled per unit fuel
cost. Recent work by Turner et al.14,15 has shown that
it is possible to introduce an additional light-alcohol
blend component, in the form of methanol, into
gasolineethanol blends in order to extend the displacement of gasoline and to allow cost competitiveness for
high-alcohol blends, thereby incentivising their use in
the growing FFV vehicle pool which can use higheralcohol blends and further incentivising the production
of such vehicles via consumer demand. Appropriate
formulation of three-component (ternary) blends of
gasoline, ethanol and methanol endows them with the
potential to serve as drop-in fuels for vehicles which
are able to operate with a given level of ethanol in gasoline. (It is recognised that gasoline is itself a complex
mixture of many hydrocarbons. It is mostly treated
here as a single-blend component with properties which
are representative of the mixture of hydrocarbons that
it contains.) In such blends the ethanol level can be varied, and cost can be made attractive to the customer by
increasing the amount of methanol used. A sensitivity
analysis of the cost of the three blend components was
undertaken by Turner et al.15 showing the conditions
under which gasolineethanolmethanol (GEM) blends
approach and drop below the energy-equivalent costs
3
of gasoline. This has to be balanced against the requirement to supply sufficient renewable ethanol.
Initial vehicle operational and material compatibility
test results, including the tail-pipe CO2 and pollutant
emissions, using such fuels have been reported in earlier
publications,14 18 together with simple economic analysis. While the initial material testing carried out by
Turner et al.18 indicated that elastomeric swelling of
the ternary GEM blends was worse than for E85, none
of the blends gave a worse performance than M85.
(MX represents a blend where X denotes the volumetric
concentration of methanol in gasoline.) This indicates
that the materials specified for the M85 vehicles which
have been used extensively in fleet trials in the USA in
the 1980s and 1990s and which are being used extensively in the Peoples Republic of China today (see the
work by Pearson and Turner19) would be compatible
with GEM blends at no significant vehicle on-cost.
The use of these iso-stoichiometric ternary blends as
transition vectors to a future economy where it may be
possible to provide renewable alcohols to supply a large
proportion of ground transportation has been discussed in several previous publications.14,19 21 This
paper focuses on the formulation and analysis of these
ternary blends and examines some of their physicochemical properties.
The original concept of ternary GEM blends was
based around the objective of formulating threecomponent blends with identical stoichiometric air-tofuel ratios (AFRs) as target two-component (binary)
blends.15 This property is essential if the drop-in fuel is
not to cause engine operation to stray outside the predetermined limits of the gravimetric AFR for which it
and its emissions treatment system were designed to
operate. The adjective iso-stoichiometric was adopted
to describe the resulting ternary blends in order to convey the objective behind their formulation.15 For the
initial blends considered in the previously reported
vehicle test programmes, it was also found that one of
the other key properties which the fuel must have in
order to avoid immediate operational problems in an
existing pre-calibrated engine, namely an approximately equal volumetric energy content (so that fuel
injector pulse durations do not have to be recalibrated
to achieve given load levels), was satisfied to a more
than acceptable degree. It should be noted that, while
much of the discussion relates to ternary blends which
are targeted at E85, it is equally possible to formulate
ternary blends to replace any other gasolineethanol
blend such as E10, E15, E20 or E50, as shown in the
second section.
In this paper the order in which the blend properties
were originally designed was inverted in order to convey the concept in a concise analytical manner. Simple
expressions are derived which quantify the volume fractions of gasoline, ethanol and methanol required to
generate a mixture having the same volumetric energy
density as a target binary blend of gasoline and
4
ethanol. The divergence from the iso-stoichiometry
condition is then quantified.
The formulation of blends where water is introduced
via some of the alcohol components is considered.
Maiorella et al.22 stated that during the ethanol fermentation process the specific ethanol productivity is
reduced with increasing ethanol concentration and is
completely halted at 87.5 g/l; if the rest of the mixture
is assumed to be water, this corresponds to a mass fraction of about 9% ethanol91% water (a volume fraction of 11%89%). This mixture can be subsequently
concentrated to mass fractions of 95.6% ethanol and
4.4% water by fractional distillation, at which point an
azeotrope is formed where the vapour in equilibrium
with the liquid has the same composition and so no further separation of the distillate can be achieved. To go
beyond this level of ethanol concentration, technologies
which use molecular sieves, membranes, solvent extraction or reduced or elevated pressure distillation are
required, adding significantly to the process energy
intensity, the well-to-tank CO2 emissions (depending
on the energy source used) and the capital cost.23,24 (At
pressures less than 9.33 kPa there is no azeotrope.)
Collura and Luyben25 stated that separation of the
water and ethanol can be responsible for up to 50% of
the process energy. As a consequence of the above factors, hydrous ethanol can be obtained at a lower cost
than that of the anhydrous product. Data given by
Makkee et al.26 showed that between 2004 and 2009
the market price of hydrous ethanol varied between
9% and 15% lower than that of anhydrous ethanol.
The effects of introducing water, at or above the
azeotropic concentration level, as a fourth component
to the ternary blend system described above, to form
what are effectively iso-stoichiometric quaternary
blends, are considered. Such mixtures will be subsequently referred to as hydrous ternary blends. It is
intended that any water present in the blend would be
introduced together with the ethanol or the various isomers of propanol and butanol which can also form the
basis of iso-stoichiometric ternary blends. These alcohols also form azeotropes with water, which prevent
them being completely dried by conventional fractional
distillation. Methanol, however, does not form an azeotrope with water. The phase equilibria of both the
anhydrous blends and the hydrous blends are discussed, and a limited set of measurements is presented
Further properties, the constancy of which would be
desirable for drop-in fuels, are also examined.
Measurements and predictions of the vapour pressure
and distillation characteristics of various blends targeted at both E85 and E15 are presented. FFVs compliant with current US and EU V emissions requirements
use an alcohol sensor in the fuel line, in addition to
software algorithms based on the vehicles tank level
sensor, in order to infer the ethanol concentration of
the fuel about to enter the engine. The response characteristics of the physical alcohol sensors to both ethanol and methanol are presented and discussed. Finally,
With the aim of formulating ternary GEM blends having a constant volumetric energy density (which could
be that of a binary blend of ethanol and gasoline, such
as E85), equation (1) can be used to calculate the
Pearson et al.
where
re QLHVe rg QLHVg
rg QLHVg rm QLHVm
rg QLHVg rQLHV
B=
rg QLHVg rm QLHVm
A=
Now, since
re QLHVe rg QLHVg \ 0
rg QLHVg rm QLHVm . 0
and
r QLHV r QLHV . r QLHV r QLHV
g
m
e
g
g
m
e
g
A is negative and less than 1. Thus, starting with a binary gasolineethanol blend which is to be turned into a
ternary GEM blend with identical volumetric energy
density rQLHV , adding methanol enables ethanol to be
removed. The methanol must be added at a slower rate
than that at which the ethanol is removed in order to
allow the volume fraction of gasoline to be increased,
Figure 2 shows that the AFRs of the range of mixtures delineated by all vertical lines in Figure 1 vary by
a maximum of 0.12% relative to that of E85 across the
range of ethanol volume fraction levels in the ternary
blend mixtures. Appendix 2 gives the relationships used
to plot these data.
Figure 3(a) to (d) shows examples of isostoichiometric blends which can substitute E85
(repeated from Figure 1 for comparison), E50, E20 and
E10. Similar blends can be formulated for butanolgasolineethanol mixtures. Again, any vertical line on the
diagrams represents a mixture with the same volumetric
energy content and essentially the same AFR, and the
limit cases of no methanol and the maximum amount
of methanol (no ethanol or butanol) permissible in the
blend are represented by the compositions given by the
vertical lines on the far right and far left of each diagram respectively. In these blends, in order to replace
ethanol with methanol, which has a lower volumetric
energy density and stoichiometric AFR, it is necessary
to replace every unit of the original alcohol which is
removed by a unit of a mixture of methanol and gasoline specifically formulated to preserve the volumetric
energy density and stoichiometric AFR. The latter
component is necessary because it has a higher volumetric energy density and stoichiometric AFR than
those of ethanol and can thus compensate for the
reduction in either property owing to the introduction
of methanol.
Figure 3. Iso stoichiometric ternary GEM blends, formulated as drop in blends for (a) E85, (b) E50, (c) E20 and (d) E10.
the energy required to dry the ethanol beyond its azeotropic point. This concept takes wet ethanol and uses it
to blend hydrous gasolineethanol mixtures, from E1
to E95. At volumetric ethanol concentrations of up to
85% these hydrous blends are potential drop-in fuels
for FFVs. Thus, hydrous E10 (hE10) made with wet
ethanol of ethanolwater of mass composition 95.6%
4.4% would contain about 0.5 mass % water; hE85
would contain about 3.5 mass % water. The concept
proposed here would be to use hydrous ethanol to produce hydrous ternary (quaternary) blends as extensions
of the type described in the second section, containing
gasoline, ethanol, methanol and water.
The analysis given in Appendix 2 shows how the
basic concept described in the second section is easily
extended to account for the use of hydrous alcohols
and focuses on obtaining blends of nominally equal
volumetric energy contents while maintaining the stoichiometric AFR of the blend within acceptable limits.
The important issue of phase separation which is often
encountered when water is present with hydrocarbon
fuels is discussed in the seventh section.
Mixtures of water in ethanol (hydrous ethanol; usually hydrous ethanol is defined as ethanol with a water
concentration greater than or equal to that at which it
forms an azeotrope (4.4 mass %)) defined by the mass
concentration as
Pearson et al.
mw
= hw, e
me + mw
hw, e g
Figure 7. Variation in the stoichiometric AFR with ethanol concentration for various water concentrations in hydrous ternary
blends at an E85 equivalent volumetric energy density.
Stoich. AFR: stoichiometric air-to-fuel ratio; vol. frac.: volume fraction.
ni
ni
= Pk
n
i 1 ni
= Pk
i
= Pk
i
mi =Mi
mi =Mi
mi =m1=Mi
11
mi =m1=Mi
mi
r Vi
= i
m
r V
k
X
ni
i
Mi
10
12
ni
n
= Pk
i
= Pk
i
ri Vi 1=Mi
ri Vi 1=Mi
ri Vi =V1=Mi
1
13
ri Vi =V1=Mi
From this equation it is clear that mixtures of components where there is a large difference in the ratio of the
component density to its molar mass will exhibit a large
difference in the values of the concentration expressed
in terms of the mole fraction and the volume fraction.
Figure 14 shows that, owing mainly to the large difference between the molar masses of the two substances,
10 vol % water in gasoline represents a mole fraction
of almost 50%, i.e. almost 50% of the molecules
Pearson et al.
Test fuels
The anhydrous mixtures studied in the present work are
those used in the vehicle test work described by Turner
et al.14,15,18 Measurements of specific hydrous blends are
not described below; only the water tolerance (to phase
separation) of the anhydrous blends is studied. More
detailed measurements of the hydrous ternary blends
described above will be presented in a further publication. Measured data for hydrous (binary) gasoline
ethanol blends have been presented by Keuken.23
Four E85- and four E15-equivalent GEM blends
were specially prepared for physicochemical analysis
and are detailed in Table 1. Ideally a RBOB should be
utilised for the gasoline fraction. An RBOB is a gasoline blending component suitable for addition of
G90:E0:M10
757.1
33.5
196.8
98.3
1.0
46.5
56.6
61.9
84.8
87
88
G88.5:E4:M7.5
758.5
33.6
194.8
97.8
1.0
49.3
57.5
61.9
84.5
83
84
pA
= xA
pA
G85:E15:M0
759.8
34.8
190.6
99.1
0.9
49.8
64.1
66.3
86.4
71
72
GEM: gaso ineethano methano ; G: gaso ine; E: ethano : M: methano ; RVP: Reid vapour pressure; NA: not avai ab e.
G44:E0:M56
776.7
35.7
194.2
99.1
0.1
81.2
81.2
81.2
90.2
NA
81
G37:E21:M42
778.0
37.4
184.3
98.6
0.9
70.2
93.0
93.0
93.9
72
72
G29.5:E42.5:M28
781.5
40.0
172.5
98.1
1.8
32.0
95.6
95.6
95.7
61
61
G15:E85:M0
787.6
50.6
102.7
99.0
0.9
4.4
99.0
99.0
99.0
40
37
kg/m3
C
C
vo %
vo %
vo %
vo %
vo %
vo %
kPa
kPa
GEM component rat o
Dens ty at 15 C
In t a bo ng po nt
F na bo ng po nt
Recovered
Res due
(Vrec/V)70
(Vrec/V)100
(Vrec/V)110
(Vrec/V)150
Measured RVP
Pred cted RVP
G100:E0:M0
756.9
34.5
194.4
99.0
0.8
32.3
52.9
58.9
84.7
65
65
B end D
B end B
B end C
RF-02-03 gaso ne
Un ts
Va ue for the fo ow ng
G87.5:E7.5:M5
758.1
33.6
196.8
98.1
1.0
52.0
59.3
62.7
84.9
78
80
B end H
B end E
B end A
B end F
B end G
Property
Table 1. Dens t es and vo at ty parameters of the base RF-02-03 gaso ne and the GEM b ends, where (Vrec/V)X represents the vo ume fract on recovered at XC.
10
14
Pearson et al.
rate program to be more suitable for a blend with a
large quantity of a single low-molecular-mass component returned the results presented in Figure 12, which
are considered to be reliable. Some of the other results
presented by Turner et al.18 are further discussed below
for completeness.
The inclusion of large quantities of a single component in a blend is known to distort the distillation profile
near to the boiling point of that single component. The
formation of azeotropes can cause further distortions,
as is known to be the case with ethanol.37 Figure 12
indicates the distillation profiles for the E85-equivalent
blends. The severe distortion of the predominantly ethanol blend of blend A is readily apparent in the figure.
The very low front-end volatility (low temperatures) is
the reason that during winter the ethanol content in E85
blends is reduced to typically 70 vol %. An adequate
cold-starting performance is thus ensured as there is a
sufficiently high gasoline component which will vaporise
at lower temperatures. With the addition of methanol
and gasoline components in the GEM blends, the distillation profile approaches that of the base gasoline. The
front-end volatilities of the methanol-only blend (blend
D) and blend C are almost identical with that of the gasoline for the first 20% recovery.
The RVP, which is an indication of the presence of
very light fractions that vaporise at low temperatures,
are also influenced by the azeotrope formed between
ethanol and the base gasoline, resulting in an increased
RVP even though the boiling point of ethanol is higher
than that of the test temperature for the RVP procedure.37 However, blend A, the high-ethanol-content
blend, has a significantly lower RVP than that of the
base gasoline. Increasing the gasoline and methanol
contents results in increases in the RVP. Blends C and
D have RVP values above that of the base gasoline. An
increased RVP is known to increase the evaporative
emissions; however, the vapour recovery systems that
were applied to the logistics chain and the use of vehicle
evaporative emissions controls, in the form of carbon
canister vapour traps, are very effective at controlling
these emissions. This small increase in the RVP for the
E85 GEM blends is not likely to impact the overall evaporative emissions severely, although the extent of this
should be considered. GEM fuels will be used in FFVs
which should not suffer from hot-weather handling
issues and this increased RVP should not negatively
impact driveability in hot conditions. Specially formulated low-volatility RBOB blending components could
of course be used to counteract these issues if required.
The E15-equivalent blends produce somewhat different trends. Figure 13 indicates that the deviations for
the iso-stoichiometric GEM blends from the base gasoline are less pronounced. All the iso-stoichiometric
GEM blends indicated higher volatilities than that of
the base gasoline with the high-methanol-content blend
H having the largest front-end deviation. Cold-weather
operation should therefore not be negatively impacted
by any of the blends.
13
The most significant impact on these isostoichiometric GEM blends is seen for the RVP. From
Table 1 it is apparent that all the alcohol-containing
blends have increased RVPs. Blend E, which contains
only ethanol, has an RVP which is 6 kPa above that of
RF-02-03 gasoline. As discussed above, an impact on
the evaporative emissions may result, but the extent of
this is likely to be limited. However, the methanolcontaining blends have significantly elevated RVP
results, which may lead to increased emissions and
increased loading of carbon canister vapour traps.
The application of gasoline fuels containing ethanol
at levels of 10% (E10) and more recently 15% (E15)
are targeted for standard vehicle applications. Modern
fuel-injected vehicles are typically immune to hotweather fuel-handling concerns. However, older vehicles with carburetted engines and some applications
with early fuel injection may be negatively affected.
The fuel volatility index (FVI), which is a composite
index of the front-end volatility parameters, is used to
control this phenomenon. The FVI takes the form
Vrec
FVI = pRV + 0:7
16
V 70
where pRV is the RVP and Vrec =Vj70 represents the
volume fraction recovered at 70 C. (Note that the usual
notation for this parameter is E70 but this has been
avoided in order to prevent confusion with the ethanol
fraction.) An alternative form of this same index is
sometimes used, namely the vapour lock index (VLI),
which is numerically 10 times greater than the FVI and
is given by
Vrec
VLI = 10pRV + 7
17
V 70
Table 2 presents the FVIs of the RF-02-03 and E15equivalent iso-stoichiometric GEM blends. Significant
increases in the FVI are apparent with the addition of
alcohol and, as the methanol content increases, the FVI
increases further. While the critical value at which hotweather handling issues would become apparent is climate dependent, the methanol-containing blends would
potentially cause some problems in regions with hot climates owing to these elevated levels. The methanolcontaining blends may be trouble free in colder climates
and, as indicated above, these effects could possibly be
counteracted to some extent with the use of specially
formulated low-volatility RBOB blending components.
14
Table 2. FVI values of the RF 02 03 gasoline and the E15 equivalent iso stoichiometric GEM blends.
Value for the following
RF 02 03
Blend E
Blend F
Blend G
Blend H
G100:E0:M0
88
G85:E15:M0
106
G87.5:E7.5:M5
114
G88.5:E4:M7.5
118
G90:E0:M10
120
GEM: gasoline ethanol methanol; G: gasoline; E: ethanol: M: methanol; FVI: fuel volatility index.
Figure 16. General volume fractions of ethanol and methanol in an admixture with gasoline, showing the boundary between the
blend stability and the unstable region in which phase separation can occur at 15 C (data corrected and replotted from the work
by Qi et al.38).
Pearson et al.
15
Figure 17. Ternary GEM blend test fuel data superimposed on the data obtained by Qi et al.,38 showing the possibility of phase
separation at 15 C with very low ethanol concentrations.
16
Pearson et al.
17
Figure 20. Physical sensor responses measured during the work conducted by Pearson et al.45 Note the different responses for
binary blends of ethanol and methanol in bulk gasoline due to the different levels of polarity of the two molecules; also note that
blends A (G15 E85 M0) and D (G44 E0 M56) have substantially the same responses.
resistance of the fuel flowing through them; these values vary widely between those for non-polar pure
hydrocarbons (of the type generally consisting of gasoline) and those for compounds with a high polarity
such as the alcohols. The performance of the virtual
sensor is used to monitor and diagnose the physical
sensor and vice versa.
Since their stoichiometric AFRs and volumetric
energy contents are essentially constant (the latter
meaning that the injector pulse widths would be identical for any calculated AFR in the EMS), ternary blends
of the type described in the present work could be
expected to be undetectable in a vehicle employing such
sensors. However, from tests on a prototype tri-FFV
employing a physical sensor, it was known that methanol and ethanol cause different responses in a physical
sensor. This is illustrated in the data presented in
Figure 20, which was gathered on the vehicle used by
Pearson et al.45 when it was fuelled with binary
gasolineethanol or gasolinemethanol fuels of various
compositions. The measured ethanol data correlate
well with information published by the supplier of this
sensor.46 From this, and other data in the literature,47
it can be discerned that, while a virtual sensor was
expected to work with the fuels in an invisible manner,
it would be dangerous to make such an assumption
automatically with a physical sensor, because the
response of the sensor for each alcohol is different
(unsurprisingly, the methanol molecule with a greater
polarity produces a greater response in the sensor than
that of the ethanol molecule).
However, inspection of Figure 20 from the standpoint of the ternary blends discussed above suggests
that the responses may not be very different for blends
with the same stoichiometry. Consider the two limiting
cases at the same stoichiometry as E85: blend A (G15
18
2.
ng
ne
nm
NRONg +
NRONe +
NRONm
n
n
n
18
Table 3. Octane number measurements for the E15 equivalent iso stoichiometric GEM blends with a low octane number gasoline
blending component.
Value for the following GEM component ratios
RON
MON
G100:E0:M0
G85:E15:M0
G87.5:E7.5:M5
G88.5:E4:M7.5
G90:E0:M10
93.3
84.0
98.0
85.8
97.8
85.5
97.6
84.8
97.0
84.5
GEM: gasoline ethanol methanol; G: gasoline; E: ethanol: M: methanol; RON: research octane number; MON: motor octane number.
Pearson et al.
19
RON
MON
Ethanol
Methanol
108.6
89.7
108.7
88.6
Conclusions
Constraints on the supply of sustainable feedstocks
limit the degree to which biofuels are able to displace
fossil fuels. The miscibility of methanol with both ethanol and gasoline enables it to be blended into mixtures
which might facilitate the increased penetration of
20
increased emissions; also the carbon canister vapour
traps may be overloaded, leading to fugitive hydrocarbon emissions.
All the fuels tested performed excellently in terms of
their inherent storage stabilities, confirming the results
of the induction period tests previously reported. The
blend stability against phase separation was evaluated
for all the anhydrous GEM blends. The blends with
only gasolineethanol have the highest water tolerance,
which decreases monotonically as the ethanol is displaced by increasing amounts of methanol and
gasoline.
The octane numbers of the ternary blends vary much
less than expected on the basis of the volume fractions
of the components. As the volume fraction of the
methanol component is increased, so the gasoline volume fraction, which has by far the lowest octane number, increases. The octane number response, however,
is much better represented using the mole fractions of
the components. According to the molar blending rules,
as the methanol and gasoline volume fractions increase
for the iso-stoichiometric GEM blends, the significant
difference in their molar masses results in a lower variation in the total alcohol mole fraction. In the current
work, E15-equivalent iso-stoichiometric blends were
prepared in order to ensure that the final blend RONs
would lie below 100 and therefore would be more accurately measured in a routine laboratory. The resulting
range of octane numbers is small, although there is a
generally decreasing trend as the methanol content
increases.
3.
4.
5.
6.
7.
8.
9.
Acknowledgement
The authors would also like to acknowledge the useful
discussions held with Richard Stone (University of
Oxford) regarding several aspects of this work.
10.
11.
12.
References
1. IEA. Advanced motor fuels annual report 2010, Interna
tional Energy Agency, Paris, France, http://www.iea.org/
impagr/cip/pdf/AMF_2010_Annual_Report.pdf (2010,
accessed 2 January 2012).
2. US Environmental Protection Agency. 40 CFR Part 80.
Regulation of fuels and fuel additives: Renewable Fuel
13.
Pearson et al.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
21
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
22
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
Appendix 1
Notation
G
h
m
mi
M
Mi
n
ni
NRON
p
pi
pRV
QLHV
Rmol
S
T
V
Vi
xi
yi
a
b
g
gi
m
r
ri
fi
Cstoich
Subscripts
e
g
m
stoich
w
ethanol
gasoline
methanol
stoichiometric
water
Abbreviations
AFR
CAFE
ECU
EMS
EX
EU
FFV
FVI
GEM
GEMW
GHG
MON
MOSCED
MX
RBOB
RFS
RON
RVP
air-to-fuel ratio
corporate average fuel economy
electronic control unit
energy management system
blend of X vol % ethanol in gasoline
European Union
flexible-fuel vehicle
fuel volatility index
gasolineethanolmethanol
gasolineethanolmethanolwater
greenhouse gas
motor octane number
modified separation of cohesive energy
density
blend of X vol % methanol in gasoline
reformulated blend-stock for oxygenate
blending
renewable fuel standard
research octane number
Reid vapour pressure
Pearson et al.
23
Appendix 2
Theoretical foundations
The density of a mixture consisting of k components
can be expressed as
r=
m
V
Pk
= Pik
i
mi
19
Vg
Ve
Vm
+
+
=1
V
V
V
Vi = V
20
k
X
Vi
=1
V
1
where k = 3 and k = 4 for ternary blends and quaternary blends respectively. For equation (20) to be valid
for the blend after mixing, the post-mixing volume
must be equal to the linear sum of the volumes of the
pre-blended components. In fact, there can be small
departures from this assumption because of the differences in the way that liquids having different molecular
sizes pack together. This effect can be quantified using
the concept of partial molar volumes discussed in
Appendix 4 but, to a first approximation, equation (20)
is sufficient to estimate the volumetric energy contents
of the mixtures of liquids considered here.
Measurements to support this assumption are discussed
briefly in the fourth section.
Using the above expressions, the density of the mixture can be written as
k
X
Vi
r=
ri
V
i 1
21
k
X
mi
i
QLHVi
k
X
ri Vi
QLHVi
r V
i 1
23
24
Vg
Ve
Vm
QLHVg + re
QLHVe + rm
QLHVm
V
V
V
26
27
29
22
25
or
30
31
24
where mji =mi is the mass fraction of species j in the mixture component i. The mass fraction of component i in
the mixture is given by
mi
r Vi
= i
m
r V
32
34
and
rQLHV = rg
35
36
can also be characterised in terms of their volume fractions by introducing the densities of the components so
that equation (36) can be rewritten as
Vw
r Ve hw, e
= e
V
rw V 1 hw, e
hw, e g
38
39
40
and
33
Vg
Ve
QLHVg + re QLHVe
V
V
Vm
Vw
QLHVm + rw
QLHVw
+ rm
V
V
rg QLHVg rQLHV
rg QLHVg rm QLHVm
Vw
r Va hw, a
= a
V
rw V 1 hw, a
and
Vg
Ve
Vm
Vw
+
+
+
=1
V
V
V
V
b
mH =m MC
=
mC =m MH
a
g
mO =m MC
=
mC =m MO
a
Ve re QLHVe
V
Vm
V
37
Vm
V
Va
C ra QLHVa
V
r
hw, a
+B
rg QLHVg 1 + a
rw 1 hw, a
41
rg QLHVg rQLHV
rg QLHVg rm QLHVm
42
and C is given by
C=
rg QLHVg
1
rm QLHVm
43
Note that the assumption of setting QLHVw = 0 in equation (35) above is open to discussion. Because the presence of water in a liquid fuel being measured in a bomb
calorimeter will change the enthalpy of vaporisation of
the mixture but will not contribute to the chemical
availability of the fuel in the test, it can be argued that
the lower heating value of the water fraction should be
negative and equal in magnitude to its enthalpy of
vaporisation. Such a modification would not make a
significant difference to the results shown in the present
work. Knowledge of the variation in the enthalpy of
vaporisation as a function of the mixture composition
would also be required. Because of the significant difference between the densities of water and the components in the blends and the effects of strong hydrogen
bonding in water (much stronger than even methanol
and ethanol), this variation is likely to be non-linear.
Appendix 3
Comparison of the volume fraction and the
mole fraction
Figure 25 shows the relationship between the volume
fraction and the mole fraction for several different alcohol fuels mixed with a standard-specification gasoline
pump fuel. It can be seen that for methanol and ethanol
Pearson et al.
there is considerable difference between the concentrations defined in terms of the volume fraction and the
mole fraction. For ethanol a 10% volume fraction in
gasoline equates to a 23% ethanol concentration by
mole fraction. In terms of the terminology defined
above, E10 on a volumetric basis could be regarded as
E23 on a molar basis, more than double the concentration implied by the volume fraction. In the same way,
E20, E50 and E85 defined on a volumetric basis become
E40, E73 and E94 respectively on a molar basis. In the
case of methanol, M10, M20, M50 and M85 defined on
a volumetric basis become M30, M49, M79 and M96
respectively on a molar basis. Therefore the mole fraction of what is referred to as M10 by volume fraction is
three times higher than might be inferred from the volume fraction. In a 50:50 volumetric mixture of methanol and gasoline, almost 80% of the molecules are
those of the alcohol.
It is also apparent from Figure 25 that for the higher
alcohols there is significantly less difference between
the mole fractions and the volume fractions. For mixtures of the particular gasoline used here and octanol
(C8H17OH) there is virtually no difference between the
volume fractions and the mole fractions. This is
because the higher density of octanol (the density of
octan-1-ol, or 1-octanol, was used) balances the effect
of the fact that the molecular mass of octanol is higher
than that of gasoline. For decanol the ratio of its density to its molar mass (decan-1-ol was used) is such that
the mole fractions of the alcohol in the gasoline are
lower than the corresponding volume fractions.
Appendix 4
Effect of the partial molar volume: anhydrous
and hydrous blends
Limitations of the simple approach to calculating the
volumetric energy of the blends in the second and third
sections are caused by the non-linear molecular packing
characteristics of the different molecules. This can be
quantified by measuring the partial molar volumes of
the various combinations. The approach defined in the
25
second section, for anhydrous blends, is sufficiently
accurate to prevent any activity of the indicator lights
of a vehicle in a current FFV, as reported by Turner
et al.14,18 The section below gives a brief description of
the concept of partial molar volumes.
The literature quantifying the effects of partial molar
volumes in fuel blends is sparse; many publications do
not acknowledge that it needs to be considered. This
may be the case where blends of fuels use components
with similar molecular sizes, or where the concentrations of the additional components are very low. The
phenomenon is raised as a possible concern in the present work because the ratio of the molecular sizes of
some of the blend components with respect to others is
very large, e.g. gasoline versus water. The effects of this
phenomenon will not be quantified here; a subsequent
publication will aim to analyse the fuel blends considered in the present work. Below, only a brief description of the concept is outlined in order to clarify its
potential importance.
The total volume of the liquid mixture components
after mixing may often depart significantly from the
sum of the volumes of the components prior to mixing.
This is because the volume occupied by a given number
of molecules in a liquid mixture depends on the identity
of the molecules that surround them. For example, when
1 mol of water is added to a huge volume of water at
25 C, the volume increases by 18 cm3. When 1 mol of
water is added to a huge volume of ethanol at 25 C,the
volume increases by only 14 cm3 because of the higher
density packing of the water molecules in this case.50 To
deal with this variation, chemists and chemical engineers
employ the concept of partial molar volumes. If volume
fractions Vi /V, rather than partial molar volumes, are
employed for mixtures of liquids then, owing to the variation in the packing effects discussed above, the partial
volumes Vi considered should refer to the volume occupied by the component in isolation (before the liquids
are mixed) and the total volume V should refer to sum
of the partial volumes in isolation rather than to the volume of the blend after mixing.
The partial molar volume is the change in the volume of a mixture on the addition of 1 mol of a substance to a large excess of the mixture50 defined as
V
Vmoli =
44
ni p, T, n9
In this equation, ni is the number of moles of component i and n9signifies that the amounts of all other substances present are constant. The value of the partial
molar volume depends on the composition of the mixture affecting the way in which the molecules being
added pack together with those in the recipient mixture. When the composition of a two-component mixture of substances A and B is changed by the addition
of dnA mol of A and dnB mol of B, the total volume of
the mixture changes by
26
V
nA
dnA +
p, T, nB
V
nB
dnB
p, T, nA
45
46
For ideal binary solutions the Gibbs energy of mixing is minimum when the mole fractions of the constituents are 0.5 as this corresponds to the state in which
the entropy change of mixing is a maximum. In nonideal solutions such as the gasolinealcohol mixtures
described above, in which the molecular interactions
between the components differ, there may be an
enthalpy change on mixing.30 There is also an additional contribution to the entropy change arising from
the tendency of molecules of one type to cluster instead
of mixing freely with the other molecules.50 In some
such situations the entropy of mixing may become positive, resulting in phase separation, as discussed above.
Appendix 6
Appendix 5
Thermodynamics of mixing
The chemical potential of mixture component A in the
liquid phase (indicated by (l)) is given by50
pA
mA l = mA l + Rmol T ln
47
pA
where mA l is the chemical potential of A as a pure
liquid. For an ideal solution the Raoult law can be combined with equation (47) to give
mA l = mA l + Rmol T ln xA
48
49
where n = nA + nB . Because
G
= S
T p, n
51
52
54
where pRVpred and pRVexp are the predicted value and the
measured value respectively of the RVP. Figure 26
shows the predicted variation in the RVP of indolene
with increasing levels of ethanol and methanol splash
blending. The experimental data plotted in Figure 26
are those from the work by Furey.31
Pearson et al.
27
Figure 26. Predicted variation in the RVP of indolene with (a) ethanol and (b) methanol blending, validated against the
experimental data from the work by Furey.31
psi: lbf/in2.
Amount (mass %)
n butane
Isopentane
Isohexane
Isooctane
Cyclopentane
2,2 dimethybutane
1 hexene
Toluene
o xylene
Ethylbenzene
m propyltoluene
n nonane
n decane
Naphthalene
Methyl tert butyl ether
n dodecane
2.2
13.18
1.66
12.71
23.27
1.97
3.36
10.90
9.90
1.99
7.50
2.93
5.92
0.83
0.07
1.61
28
Figure 27. (a) Predicted indolene, (b) predicted indolene + 10 vol % ethanol and (c) predicted indolene + 10 vol % methanol
distillation curves, validated against the experimental data from the work by Furey.31
Pearson et al.
29
characteristics of both the base fuel and the non-ideal
interactions of the base fuel with ethanol and methanol
with good accuracy.