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Short communication

Relationships derived from physical properties

of vegetable oil and biodiesel fuels
Ayhan Demirbas *

Sila Science, Trabzon, Turkey

Received 22 June 2007; accepted 13 August 2007

Available online 5 September 2007

Abstract

The aim of this study was to estimate mathematical relationships between higher heating value (HHV) and viscosity, density or flash
point measurements of various biodiesel fuels. The HHV is an important property defining the energy content and thereby efficiency of
fuels, such as vegetable oils and biodiesels. The biodiesels were characterized for their physical and main fuel properties including vis-
cosity, density, flash point and higher heating value. The viscosities of biodiesels (2.8–5.1 mm2/s or cSt at 311 K) were much less than
those of pure oils (23–53 mm2/s at 311 K), and their HHVs of approximately 41 MJ/kg were 10% less than those of petrodiesel fules
(46 MJ/kg). Compared to No. 2 diesel fuel, all of the vegetable oil methyl esters were slightly viscous. The density and flash point values
of vegetable oil methyl esters are highly lower than those of vegetable oils. The HHVs of vegetable oils and their biodiesels were measured
and correlated using linear least square regression analysis. There is high regression between viscosity and higher heating value for veg-
etable oil and biodiesel samples. An increase in density from 848 to 885 g/L for biodiesels increases the viscosity from 2.8 to 5.1 cSt and
the increases are highly regular. There is high regression between density and viscosity values vegetable oil methyl esters. The relation-
ships between viscosity and flash point for vegetable oil methyl esters are considerably regular.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Biodiesel; Higher heating value (HHV); Viscosity

1. Introduction engine problems. The disadvantages of vegetable oils as

The scarcity of conventional fossil fuels and the concern
of environmental protection, the utilization of biofuel from
biorenewable resources have attracted increasing world-
wide interest [1–3]. With recent increases in petroleum
prices, there is renewed interest in vegetable oil and their
derivatives as alternative fuels for diesel engines [4]. As
an alternative fuel vegetable oil is one of the renewable
fuels. Vegetable oils have become more attractive recently
because of its environmental benefits and the fact that it
is made from renewable resources [5–10]. The major prob-
lem associated with the use of pure vegetable oils as fuels,
for Diesel engines are caused by high fuel viscosity in com-
pression ignition and resulting injector fouling and other
*
Tel.: +90 462 230 7831; fax: +90 462 248 8508.
E-mail address: ayhandemirbas@hotmail.com
diesel fuel are: (a) higher viscosity, (b) higher pour point,
(c) higher flash point, (d) higher cloud point, (e) higher den-
sity, and (f) the reactivity of unsaturated hydrocarbon
chains [11–15].
The vegetable oils are all extremely viscous with viscos-
ities ranging from 9 to 17 times greater than petroleum die-
sel fuel. Vegetable oils and their derivatives, especially
(m)ethyl esters, commonly referred to as ‘‘biodiesel,’’ are
prominent candidates as alternative diesel fuels. Biodiesel
is generally made of methyl esters of fatty acids produced
by the transesterification reaction of triglycerides with
methanol in the presence alkali as a catalyst [16]. The pur-
pose of the transesterification process is to lower the viscos-
ity of the oil. Among the alcohols that can be used in the
transesterification reaction are methanol, ethanol, propa-
nol, butanol and amyl alcohol. Methanol and ethanol are
used most frequently, ethanol is a preferred alcohol in

0016-2361/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2007.08.007
1744 A. Demirbas / Fuel 87 (2008) 1743–1748

the transesterification process compared to methanol cup and a thermostat was used to measure the viscosity
because it is derived from agricultural products and is of all samples. The kinematic viscosity measurements were
renewable and biologically less objectionable in the envi- carried out as mm2/s or cSt at 311 K temperature. The tem-
ronment, however methanol because of its low cost and peratures were checked with a digital thermometer within
its physical and chemical advantages. The transesterifica- the thermostat and the viscosimeter. At the beginning of
tion reaction can be catalyzed by alkalis [9,17–19], acids each measurement a volume of 50 ml of the sample was
[20], or enzymes [21–24]. filled into the measuring cup.
A novel process of biodiesel fuel production has been Density measurements were carried out using a pycnom-
developed by a non-catalytic supercritical fluids (methanol eter at a temperature of 311.15 ± 0.05 K; the pycnometer
and ethanol) method. The transesterfication of triglycerides of capacity about 25 mL being calibrated with water [32].
by supercritical methanol, ethanol, propanol and butanol, Flash point measurements were carried out using a Koeh-
has proved to be the most promising process [25,26]. ler mark apparatus.
The standard measure of the energy content of a fuel is Relative standard deviation (RSD) for all measurements
its heating value (HV), sometimes called the calorific value was 0.9–1.2% for three separate determinations.
or heat of combustion. The heating value is obtained by the
complete combustion of a unit quantity of solid fuel in an
oxygen-bomb colorimeter under carefully defined condi- 3. Results and discussion
tions. The gross heat of combustion or higher heating value
(GHC or HHV) is obtained by oxygen-bomb colorimeter The viscosity, density, flash point, and higher heating
method as the latent heat of moisture in the combustion value (HHV) measurements of twenty two vegetable oils
products is recovered. The higher heating value is one of and their methyl esters are given in Table 1. The viscosity,
the most important properties of a fuel. density, flash point, and higher heating value (HHV) mea-
Higher heating values of biomass-derived fuels have surements of fourteen methyl esters of various vegetable
been estimated using their proximate and ultimate analysis oils are tabulated in Table 2.
data [27–29]. It has also been shown that an estimate of the Viscosity is a measure of the internal friction or resis-
heating values of vegetable oils can be calculated using tance of an oil to flow. As the temperature of oil is
saponification and iodine data of the oils [30,31]. The increased, its viscosity decreases and it is therefore able
higher heating value of a fuel increases with increasing car- to flow more readily. Viscosity is the most important prop-
bon number in fuel molecules and also increases as the erty of biodiesel since it affects the operation of fuel injec-
ratio of carbon and hydrogen to oxygen and nitrogen tion equipment, particularly at low temperatures when the
increases [28]. increase in viscosity affects the fluidity of the fuel. High vis-
Fuel properties of vegetable oils were characterized by cosity leads to poorer atomization of the fuel spray and less
determining its viscosity, density, cetane number, cloud
and pour points, distillation range, flash point, ash content, Table 1
sulfur content, carbon residue, acid value, copper corrosion Viscosity, density flash point and higher heating value (HHV) measure-
and HHV [11]. ments of twenty two vegetable oils
The objective of this study was to estimate mathematical Vegetable oil Viscosity Density Flash point HHV
relationships between higher heating value (HHV) and vis- (cSt) (g/L) (K) (MJ/kg)
cosity, density or flash point measurements of various bio- Ailanthus 30.2 916 513 39.44
diesel fuels from various vegetable oils by transesterification Bay laurel 23.2 921 499 39.30
method. Beech 34.6 915 515 39.59
Beechnut 38.0 912 533 39.82
Corn 35.4 914 532 39.66
2. Experimental Cottonseed 33.5 915 524 40.38
Crambe 53.0 902 557 39.83
The vegetable oils were obtained from commercial Hazelnut 24.0 920 503 39.33
sources and used without further purification. The samples Linseed 27.2 921 520 39.50
Mustard oil 33.8 913 518 39.57
were converted to methyl esters by alkali catalytic and non-
Olive 29.8 918 504 39.50
catalytic supercritical methanol transesterification methods. Palm 24.1 923 501 39.74
The HHVs of the vegetable oils and their methyl esters Peanut 39.6 908 543 39.85
were measured in a bomb calorimeter according to ASTM Poppy seed 42.4 907 538 39.73
D2015 standard method [30]. An oxygen-bomb was pres- Rapeseed 37.3 912 531 39.52
Safflower seed 31.3 914 531 39.79
surized to 3 MPa with an oxygen container. The bomb
H.O.Safflower 41.2 906 548 39.51
was fired automatically after the jacket and bucket temper- Sesame 35.5 913 533 39.63
atures equilibrated to within acceptable accuracy of each Soybean 32.6 914 528 39.44
other. Spruce 35.6 914 513 39.57
Each sample was used for viscosity and density measure- Sunflower seed 33.9 916 535 39.59
Walnut 36.8 912 524
ments. A Redwood No. 1 viscosimeter with a measuring
 A. Demirbas / Fuel 87 (2008) 1743–1748 1745

Table 2 The HHV is an important property defining the energy

Viscosity, density, flash point and higher heating value (HHV) measure- content and thereby efficiency of fuels, such as vegetable
ments of fourteen oil methyl esters
oils and biodiesels. Fuel properties for the combustion
Methyl ester Viscosity Density Flash point HHV analysis of vegetable oils can be grouped conveniently into
(cSt) (g/L) (K) (MJ/kg)
physical, chemical and thermal properties. Physical proper-
Cottonseed oil 3.75 871 455 41.18 ties include viscosity, density, cloud point, pour point, flash
Corn oil 3.62 873 427 41.14
Crambe oil 5.12 848 463 41.98
point, boiling range, freezing point and refractive index.
Hazelnut oil 3.59 875 425 41.12 There exist a number of correlations for estimating the
Linseed oil 2.83 885 415 40.84 HHV of vegetable oils based upon its physical properties
Mustard oil 4.10 866 442 41.30 [11,12,31].
Olive oil 4.18 860 447 41.35 Figs. 1 and 2 show the correlations between viscosity
Palm oil 3.94 867 434 41.24
Rapeseed oil 4.60 857 453 41.55
and higher heating value (HHV) for vegetables oils and
Safflower oil 4.03 866 440 41.26 biodiesels, respectively. As can be seen from Figs. 1 and
Sesame oil 3.04 880 418 40.90 2, the HHVs of vegetables oils and biodiesels increase with
Soybean oil 4.08 865 441 41.28 viscosity. For the correlation of fuel higher heating values
Sunflower oil 4.16 863 439 41.33 related to their viscosities, densities and flash points, regres-
Walnut oil 4.11 864 443 41.32
sion analysis was performed. The HHVs of vegetable oils
and their biodiesels were measured and correlated using
linear least square regression analysis. Equations were
accurate operation of the fuel injectors. The viscosity val- developed for the calculation of the HHV of vegetable oils
ues of vegetable oils are between 23.2 and 53.0 mm2/s and biodiesels from their viscosity (VS), density (DN) and
whereas those of vegetable oil methyl esters are between flash point (FP). The equations between viscosity and
2.8 and 5.1 mm2/s. The viscosity values of vegetable oil higher heating value are
methyl esters highly decreases after transesterification pro-
cess. Compared to No. 2 diesel fuel, all of the vegetable oil for vegetable oils:
methyl esters were slightly viscous. HHV ¼ 0:0317VS þ 38:053 ð1Þ
Density is another important property of biodiesel. It is
the weight of a unit volume of fluid. Specific gravity is the for biodiesels:
ratio of the density of a liquid to the density of water. Spe- HHV ¼ 0:4625VS þ 39:450 ð2Þ
cific gravity of biodiesels ranges between 848 and 885 g/L.
Fuel injection equipment operates on a volume metering with coefficient of regression (r) values of 0.9435, and
system, hence a higher density for biodiesel results in the 0.9677, respectively. There is high regression between vis-
delivery of a slightly greater mass of fuel. An increase in cosity and higher heating value for vegetable oil and bio-
density from 848 to 885 g/L for biodiesels increases the vis- diesel samples. The correlations may be used for HHV
cosity from 2.8 to 5.1 cSt and the increases are highly estimation of mixtures of biodiesels obtained from vegeta-
regular. ble oils.
Table 3 shows viscosity, density and cetane number Figs. 3 and 4 show the correlations between viscosity
(CN) measurements of seven methyl ester biodiesels given and density for vegetables oils and biodiesels, respectively.
in the literature [33–37]. The CN is a measure of ignition As can be seen from Figs. 3 and 4, the viscosities of
quality of diesel fuel. The higher the CN, the easier the fuel
ignites when it is injected into the engine. The higher the
40.6
CN is the more fuel-efficient the fuel. Biodiesel has a higher
CN than petrodiesel because of its higher oxygen content 40.4
[38].
Higher heating value, MJ/kg

40.2

40
Table 3
Viscosity, density and cetane number measurements of seven methyl ester
39.8
biodiesels
Source Viscosity cSt at Density g/L at Cetane References 39.6
313.2 K 288.7 K number
Sunflower 4.6 880 49 [33] 39.4
Soybean 4.1 884 46 [34]
Palm 5.7 880 62 [33] 39.2
20 25 30 35 40 45 50 55
Peanut 4.9 876 54 [35]
Cottonseed 3.8 874 46 [36] Viscosity, cSt
Babassu 3.6 – 63 [35]
Fig. 1. Correlation between viscosity and higher heating value for
Tallow 4.1 877 58 [37]
vegetables oils.
1746 A. Demirbas / Fuel 87 (2008) 1743–1748

42.1 890
Higher heating value, MJ/kg

41.8 880

Density, g/L
41.5 870

41.2 860

40.9 850

40.6 840
2.8 3.3 3.8 4.3 4.8 5.3 2.8 3.3 3.8 4.3 4.8 5.3
Viscosity, cSt Viscosity, cSt

Fig. 2. Correlation between viscosity and higher heating value for Fig. 4. Correlation between viscosity and density for biodiesels.
biodiesels.

470
vegetables oils and biodiesels decrease with density. The
equations between viscosity and density are 460
for vegetable oils:
450
VS ¼ –0:7328DN þ 938:57 ð3Þ
Flash point, K

for biodiesels: 440

VS ¼ –16:155DN þ 930:78 ð4Þ 430

with coefficient of regression (r) values of 0.9398, and
0.9902, respectively. There is high regression between vis- 420
cosity and density for biodiesel samples.
Fig. 5 shows the correlation between viscosity and flash 410
2.8 3.4 4 4.6 5.2
point for biodiesels. The equation between viscosity and
Viscosity, cSt
flash point for biodiesels is
Fig. 5. Correlation between viscosity and flash point for biodiesels.
VS ¼ 22:981FP þ 346:79 ð5Þ
with coefficient of regression (r) value of 0.9819. There is HHV ¼ –0:0259 þ 63:776 ð6Þ
considerably high regression between viscosity and flash
point for biodiesel samples. with coefficient of regression (r) value of 0.7982. There is
Fig. 6 shows the correlation between density and higher considerably low regression between density and higher
heating value for biodiesels. The equation between viscos- heating value for biodiesel samples. The higher heating val-
ity and flash point for biodiesels is ues decrease with increasing density for the biodiesels.

42
925

920
Higher heating value, MJ/kg

41.7

915
Density, g/L

41.4
910

905 41.1

900
40.8
895 840 850 860 870 880 890
20 25 30 35 40 45 50 55 Density, g/L
Viscosity, cSt
Fig. 6. Correlation between density and higher heating value for
Fig. 3. Correlation between viscosity and density for vegetables oils. biodiesels.

42
Higher heating value, MJ/kg
41.7
41.4
41.1
40.8
410 420 430 440
Flash point, K
Fig. 7. Correlation between flash point and higher heating value for
biodiesels.
Fig. 7 shows the correlation between flash point and
higher heating value for biodiesels. The equation between
flash point and higher heating value for biodiesels is
HHV ¼ 0:021FP þ 32:12
with coefficient of regression (r) value of 0.9530. There is
considerably high regression between flash point and high-
er heating value for biodiesel samples. The higher heating
values increase with increasing flash point for the
biodiesels.
Viscosity is one of the most important parameters
required in the design of combustion process. From the
physicochemical point of view, viscosity means the resis-
tance of one part of the fluid to move relative to another
one. Therefore, viscosity must be closely correlated with
the structural parameters of the fluid particles. The viscos-
ity slightly decreases with increased degree of unsaturation
and rapidly increases with polymerisation. The viscosity
almost linearly decreases as the iodine value increases.
On the other hand, no correlation was found for the depen-
dence of viscosity on saponification value, which character-
ises the chain length of fatty acids [39].
The length of the fatty acid chain was shown to have a
marked influence on the viscosity. The viscosity of the sys-
tems is also influenced by the degree of unsaturation. One
double bond was shown to increase viscosity, whereas two
or three double bonds caused a decrease in the viscosity of
the systems [40].
Structural features that influence the physical and fuel
properties of a fatty ester molecule are chain length, degree
of unsaturation, and branching of the chain [41]. Kine-
matic viscosity increases with chain length (number of car-
bon atoms) and with increasing degree of saturation of
either the fatty acid or alcohol moiety in a fatty ester or
in an aliphatic hydrocarbon. The increase in kinematic vis-
cosity over a certain number of carbons is smaller in ali-
phatic hydrocarbons than in fatty compounds. The
kinematic viscosity of unsaturated fatty compounds
A. Demirbas / Fuel 87 (2008) 1743–1748 1747
strongly depends on the nature and number of double
bonds with double bond position affecting viscosity less.
On the other hand, factors such as double bond configura-
tion influence viscosity (cis double bond configuration giv-
ing a lower viscosity than trans) while double bond
position affects viscosity less. Terminal double bonds in ali-
phatic hydrocarbons have a comparatively small viscosity-
reducing effect. Branching in the alcohol moiety does not
significantly affect viscosity compared to straight-chain
analogues. Free fatty acids or compounds with hydroxy
groups possess significantly higher viscosity [42].
4. Conclusion
450 460
Equations have been developed to calculate higher heat-
ing values (HHVs) of various vegetable oils and their bio-
diesels from their viscosity, density or flash point
measurements.
The vegetable oils are all extremely viscous with viscos-
ities ranging from 9 to 17 times greater than petroleum die-
sel. Biodiesel, an alternative diesel fuel, is made from
renewable biological sources such as vegetable oils and ani-
ð7Þ mal fats by transesterification reaction using methanol or
ethanol. The purpose of the transesterification process is
to lower the viscosity of the oil.
The properties of biodiesel are close to diesel fuels. Fuel
properties of vegetable oils and biodiesels are characterized
by determining its viscosity, density, cetane number, cloud
and pour points, distillation range, flash point, ash content,
sulfur content, carbon residue, acid value, copper corrosion
and HHV according to ISO norms.
The heating values of the vegetable oils and their methyl
esters (biodiesels) can be calculated by using the viscosity,
density and flash point obtained from simple physical mea-
surements. The experimental determination of heating
value and an element (C, H, O) content requires special
instrumentation, whereas physicochemical data can be
obtained relatively easily by using common laboratory
equipment.
There is high regression between HHV and viscosity val-
ues of vegetable oils and their methyl esters. An increase in
density from 848 to 885 g/L for vegetable oil methyl esters
or biodiesels increases the viscosity from 2.83 to 5.12 mm2/s
and the increases are highly regular.
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