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Basic properties of palm oil biodieseldiesel blends

Pedro Benjumea a,*, John Agudelo b, Andres Agudelo b
a
Alternative Fuels Group, Energy Institute, Faculty of Mines, Universidad Nacional de Colombia Sede Medelln, Colombia
b
Group of Energy Ecient Management GIMEL, Engineering Faculty, Universidad de Antioquia, Colombia

Received 16 May 2007; received in revised form 24 October 2007; accepted 12 November 2007
Available online 21 December 2007

Abstract

The basic properties of several palm oil biodieseldiesel fuel blends were measured according to the corresponding ASTM standards.
In order to predict these properties, mixing rules are evaluated as a function of the volume fraction of biodiesel in the blend. Kays mixing
rule is used for predicting density, heating value, three dierent points of the distillation curve (T10, T50 and T90), cloud point and cal-
culated cetane index, while an Arrhenius mixing rule is used for viscosity. The absolute average deviations (AAD) obtained were low,
demonstrating the suitability of the used mixing rules. It was found that the calculated cetane index of palm oil biodiesel obtained using
ASTM D4737 is in better agreement with the reported cetane number than the one corresponding to the ASTM D976. This result is most
likely due to the fact that the former standard takes into account the particular characteristics of the distillation curve.
2007 Elsevier Ltd. All rights reserved.

Keywords: Palm oil biodiesel; Blends; Basic properties; Mixing rules

1. Introduction ber, and lower volatility and heating value compared to

Biodiesel is currently the most widely accepted alter-
native fuel for diesel engines due to its technical, envi-
ronmental and strategic advantages. It has enhanced
biodegradability, reduced toxicity and improved lubricity
in comparison with conventional diesel fuels. In addition,
this biofuel is completely miscible with petroleum diesel,
allowing the blending of these two fuels in any proportion.
Biodiesel can be used neat or blended in existing diesel
engines without signicant modications to the engine.
However, dierences in the chemical nature of biodiesel
(mixture of mono-alkyl ester of saturated and unsaturated
long chain fatty acids) and conventional diesel fuel (mix-
ture of paranic, naphthenic and aromatic hydrocarbons)
result in dierences in their basic properties, aecting
engine performance and pollutant emissions. Biodiesel,
produced from any vegetable oil or animal fat, generally
has higher density, viscosity, cloud point and cetane num-
*
Corresponding author. Tel.: +574 425 5319; fax: +574 234 1004.
E-mail address: pbenjume@unalmed.edu.co (P. Benjumea).
commercial grades of diesel fuel [19].
It is important to know the basic properties of biodiesel
diesel blends. Some of these properties are required as
input data for predictive and diagnostic engine combustion
models. Additionally, it is necessary to know if the fuel
resulting from the blending process meets the standard
specications for diesel fuels. Given the diculty of obtain-
ing the basic properties of the blend by measurement, the
ability to calculate these properties using blending or mix-
ing rules is very useful. Such an approach allows an a priori
estimation of blend properties as a function of composition
and pure component values.
Clements [10] proposed blending rules for estimating the
density, heating value, viscosity, cetane number and cloud
point of biodiesel as a function of its methyl esters prole.
By comparing predicted values with experimental data, he
found that the typical average errors were less than 2%,
with the exception of viscosity, where the average error
was 10%. Similar blending rules to those proposed by Cle-
ments for calculating properties of methyl ester blends have
also been used by other researchers for estimating proper-
ties of biodieseldiesel blends.

0016-2361/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2007.11.004
2070 P. Benjumea et al. / Fuel 87 (2008) 20692075

Tat and Van Gerpen [11] presented experimental data than empirical correlations, which would be valid only
for kinematic viscosity of a commercial soybean oil biodie- for the specic blends tested.
sel and its blends with grade No. 1 and No. 2 diesel fuels at
75%, 50% and 20% biodiesel (by weight), from a tempera-
2. Methods
ture close to the biodiesel melting point up to 100 C.
Results showed that viscosity increased with the increase
2.1. Blend preparation
in the percentage of biodiesel. The temperature-dependent
viscosity behaviour of the blends was similar to that of neat
The biodiesel used in this work was produced in a pilot
fuels. Blend viscosities were estimated by means of a blend-
plant by basic methanolysis of crude palm oil using a meth-
ing rule, similar to the one proposed by Arrhenius and
anol/oil molar ratio of 12:1, with 0.6% sodium hydroxide
described by Grunberg and Nissan [12]. The maximum dif-
by weight as the catalyst. The reaction temperature and
ferences between predicted and measured viscosities were
time were 60 C and 1 h, respectively. The methyl ester
less than 2.05% and 3.74% of the measured values for the
composition of palm oil biodiesel (POB) was determined
biodiesel blends with No. 2 and No. 1 diesel fuels,
by gas chromatography (see Table 1). The commercial
respectively.
grade No. 2 diesel fuel (D) used had an elemental compo-
Tat and Van Gerpen [13] carried out a study on the den-
sition by weight of 87.2% carbon, 12.8% hydrogen and
sity of blends similar to that referenced for viscosity [11].
0.0225% sulphur, and an aromatic content of 29.3% (13%
The results indicated a linear type specic gravitytemper-
monoaromatics, 13.3% diaromatics and 3% polyaromat-
ature relationship for the soybean oil biodieseldiesel
ics). Although several blends with a wide composition spec-
blends that was similar to that of the pure diesel fuels. A
trum were prepared by splash blending [17], most of the
mass weighted average was used to estimate blend specic
tests were carried out with B5 (5% POB-95% D by volume)
gravities. This simple approach is known in the hydrocar-
and B20 blends, due to their widespread use. Neat fuels are
bon industry as Kays mixing rule [14].
designated as B100 and B0, respectively. Blends were pre-
Yuan, Hansen and Zhang [15] carried out a study with
pared on a volume basis at 25 C. Although blend prepara-
density similar to that of Tat and Van Gerpen [13], using
tion on a weight basis has the advantage that weight
three types of biodiesel (two produced from soybean oil
fraction does not change with temperature, the common
and another more saturated biodiesel prepared from yellow
practice in the fuel industry is to carry out the mixing pro-
grease). These were blended with grade No. 2 diesel fuel at
cess on a volume basis at the ambient temperature of the
75%, 50% and 25% biodiesel (by weight), and tested from
blending location, usually a wholesale commercial plant.
close to the biodiesel crystallization onset temperature up
For this reason, the option selected in this work was to
to 100 C. The measurements indicated that all biodiesel
use blending rules as a function of volumetric fractions.
fuels and their blends with No. 2 diesel fuel had a linear
specic gravitytemperature relationship similar to pure
diesel fuel. The densities of the blends estimated by Kays 2.2. Experimental
mixing rule showed an average absolute deviation (AAD)
of less than 0.43% for all tested fuels in the temperature Cloud point was measured according to ASTM D2500
range studied. [18]. Density was determined following ASTM 287 [19]
Joshi and Pegg [16] presented experimental data for using calibrated glass API gravity hydrometers. A mineral
dynamic viscosity and cloud and pour points of biodiesel oil bath with a temperature control precision of 0.02 C
derived from ethyl esters of sh oil and its blends with was used for measuring density at dierent temperatures,
No. 2 diesel fuel at 80%, 60%, 40% and 20% biodiesel (by from close to the cloud point of POB up to 100 C. Kine-
volume). The measurements of the cold ow properties of matic viscosity was determined according to ASTM D445
the blends were correlated as functions of biodiesel content [20] using a capillary tube viscometer. The calibration con-
using empirical second-order polynomials, giving regres- stant of the viscometer supplied by the manufacturer is
sion coecients of 0.996 and 0.995 for the predicted cloud given only for temperatures of 40 and 100 C, so the con-
and pour points, respectively. stant for all other temperatures was linearly interpolated
The present paper presents experimental density and vis- or extrapolated from these values. Both density and kine-
cosity data as a function of temperature, together with the
heating value, distillation curves and cloud point for palm Table 1
oil biodiesel and its blends with No. 2 diesel fuel. Addition- Chemical composition of palm oil biodiesel by GC
ally, the calculated cetane index of the tested neat fuels and Fatty acid methyl ester Mass percent
their blends is obtained by empirical correlations recom-
C12:0 0.267
mended for hydrocarbon fuels. The aim of this work is to C14:0 1.434
evaluate mixing rules for calculating the basic properties C16:0 46.130
of palm oil biodieseldiesel fuel blends as a function of bio- C18:0 3.684
diesel content (volume fraction). This approach is more C18:1 37.470
C18:2 11.020
likely to be applicable to other biodiesel fuels and blends
 P. Benjumea et al. / Fuel 87 (2008) 20692075 2071

matic viscosity were measured from the cloud point of POB
up to 100 C. High, or gross heating value was determined
using an IKA automated bomb calorimeter, following
ASTM D240 [21]. All fuels tested were distilled following
the procedure established by ASTM D86 [22]. In addition
to the initial and nal boiling points, temperatures for dis-
tilled percentage multiples of 10 were also registered. The
temperature values measured were normalized to standard
atmospheric pressure by means of the SidneyYoung cor-
relation, as recommended by ASTM D86. The calculated
cetane index for the fuels tested was determined as a func-
tion of their densities and distillation curve data using the
empirical correlations recommended by ASTM D976 [23]
and D4737 [24].
3. Results and discussion
3.1. Basic properties of pure fuels
Experimental data on the basic properties of palm oil
biodiesel and diesel fuel are presented in Table 2. The most
critical property of POB is its high cloud point, due to its
high content of long chain, highly saturated methyl esters
(see Table 1). At 16 C POB starts to form crystals. At
around 12 C, these crystals may plug lters and fuel lines.
These faulty cold ow properties of POB limit its utiliza-
tion as a neat fuel or in rich biodiesel blends in cold cli-
mates or in the winter season. POB is denser, slightly
more viscous, and has a narrower boiling interval than die-
sel fuel, indicating that the fatty acid methyl esters in bio-
diesel have similar boiling points. Diesel fuel, meanwhile,
is composed of a wide variety of hydrocarbons with dier-
ent volatilities. This explains why biodiesel is denser than
diesel fuel despite having a lower nal boiling point. POB
has a gross heating value lower than diesel fuel due to
the presence of oxygen in the methyl ester molecules. This
dierence in heating values, expressed as energy per unit
mass, is slightly reduced when it is reported as energy per
unit volume, given the greater density of POB. As a result
of these dierences, the calculated cetane index for POB is
higher than for diesel fuel; this agrees with the tendency
reported by several researchers for both cetane numbers
and CCI [1,8,9].
3.2. Eect of temperature
In order to analyze the eect of temperature on density
and kinematic viscosity of the pure fuels and their blends,
the experimental data were tted by means of statistical
regressions.
Fig. 1 shows the eect of temperature on density (q) for
pure fuels and B5 and B20 blends. In the temperature range
studied there were no qualitative dierences in the behavior
of the fuels tested. Experimental data were correlated by
linear regressions, presented in Table 3. The regression
coecients (R2) were always greater than 0.99, indicating,
as expected, that linear regression accurately represents
the densitytemperature relationship for the fuels tested.
Viscositytemperature curves for pure fuels and several
blends are shown in Fig. 2. As can be seen in this gure,
the curves for diesel fuel and for the blends exhibit a similar
trend for temperature variation, and these curves are prac-
tically identical due to the small dierences in the viscosities
of the pure fuels.
The variation of kinematic viscosity (g) with tempera-
ture for dierent types of uids has been commonly repre-
sented by means of Andrade type equations, such as the
following [11,25]:
2
g eAB=T C=T 1
The constants (A, B, C) and the regression coecients
(R2) for each regression curve shown in Fig. 2 are presented
in Table 4.

Table 2
Basic properties of No. 2 diesel fuel and palm oil biodiesel
Properties Units ASTM Diesel Palm oil
standard fuel No. 2 Biodiesel Fig. 1. Variation of blend density with temperature.
3
Density at 25 C kg/m D1298 853.97 864.42
Mass high heating value MJ/kg D240 45.273 39.837
Volume high heating value MJ/m3 D240 38662 34436
(25 C) Table 3
Cloud point C D2500 5.0 16.0 Linear regressions parameters for fuel densities
Cold lter plugging point C D6371 6.0 12.0 Fuel type Linear regression q a bT
Kinematic viscosity at 40 C mm2/s D445 4.33 4.71
a b R2
Initial boiling point C D86 181.5 302.2
Temperature at 50% recovered C D86 284.9 326.5 B100 882.6689646 0.7342772415 0.996686
Final boiling point C D86 384.3 348.9 B20 876.6406154 0.7115968933 0.997702
Calculated cetane index D4737 46.3 57.3 B5 873.0569269 0.6920565595 0.994305
D976 47.5 50.0 B0 869.6231871 0.6792453596 0.997307
2072 P. Benjumea et al. / Fuel 87 (2008) 20692075

these modications, Eq. (3) for a binary mixture takes the

Fig. 2. Variation of blend Kinematic viscosity with temperature.
3.3. Eect of biodiesel content
Mixing rules are used for estimating the basic properties
of blends as a function of pure fuel properties and biodiesel
content. The suitability of these rules is evaluated by means
of the absolute average deviation (AAD), calculated as
NP  
100 X  uEXP  uPR 
AAD 2
NP i1  uEXP 
where NP is the number of experimental points, u is the
property to be predicted and the subscripts are EXP for
experimental and PR for predicted.
The GrunbergNissan mixing rule is widely used for
predicting viscosity of liquid mixtures [26]:
X
n n X
X n
ln lB xi ln li xi xj Gij
i i j shown in Fig. 4. As was expected, density is directly pro-
where lB is the mean absolute viscosity of the blend, li the
absolute viscosity of pure ith component, xi and xj the mole
fractions of the ith and jth components, Gij the interaction
parameter (Gij = 0, for i = j), and n the number of
components.
When the components of a mixture have similar chemi-
cal structure it is expected that they do not interact with
each other and consequently the interaction parameter in
Eq. (3) can be neglected. Biodieseldiesel fuel blends can
be assumed to behave this way because both liquids are
non-polar, completely miscible, and when blended their
volumes are practically additive. In this work the volume
fraction and the kinematic viscosity are used instead of
the mole fraction and absolute viscosity, respectively. With
form of a geometric volume average (Arrhenius-type
equation):
ln gB V POB  ln gPOB V D  ln gD 4
In the above equation, V is the volume fraction and the
subscripts are B for blend, POB for biodiesel and D for die-
sel fuel.
For the remaining properties, Kays mixing rule is used:
X
n
uB xi ui 5
i
where uB is the property of the blend and ui is the respec-
tive property of the ith component. Using volume fraction
instead of molar fraction, Eq. (5) for a binary mixture takes
the form of an arithmetic volume average:
uB V POB  uPOB V D  uD 6
3.3.1. Viscosity
Fig. 3 shows the eect of biodiesel content on the viscos-
ity of the blends tested for three representative tempera-
tures. As can be seen in this gure, viscosity slightly
increases with biodiesel content. The AADs obtained using
the selected mixing rule for estimating blend viscosity were
1.07%, 0.64% and 0.72% for the data corresponding to 16,
40 and 100 C, respectively.
3.3.2. Density
3 The variation in blend density with biodiesel content is
portional to biodiesel content. The AADs obtained using
Kays mixing rule to estimate blend densities were 0.13%,
0.15% and 0.09% for the data corresponding to 16, 40
and 100 C, respectively.
3.3.3. Heating value
Low heating values (LHV) were calculated from the
measured high heating values (HHV), taking into account
the elemental composition of the pure fuels and the
enthalpy of vaporization of water. As can be seen in
Fig. 5, the LHV of blends decreases in direct proportion

Table 4
Regression parameters for viscosity
2
Fuel type Regression equation g eAB=T C=T

A B C R2
B100 0.364206158 55.22818898 416.2888996 0.988622
B30 0.192149860 60.09025836 462.560271 0.989173
B20 0.162400318 61.85122113 491.0603185 0.962320
B5 0.220089863 56.0562369 409.7122203 0.978609
B0 0.142954422 60.16294716 456.709883 0.98695
Fig. 3. Variation of blend kinematic viscosity with biodiesel content.
 P. Benjumea et al. / Fuel 87 (2008) 20692075
Fig. 4. Variation of blend density with biodiesel content.
to the biodiesel content. The AAD obtained using Kays
mixing rule to estimate the LHV of blends was 0.19%.
3.3.4. Cloud point
Fig. 6 shows the eect of biodiesel content on the cloud
point (TCP) of the pure fuels and on a wide spectrum of
blends. Although the mixing rule allowed an excellent
match of the experimental points (see Fig. 6), the AAD
obtained was quite high (15.2%). This happened due to
the temperature scale used. Changing degrees Celsius to
Kelvin gives an AAD of 0.19%.
3.3.5. Distillation curve points
Fig. 7 shows the distillation curves for pure fuels and for
B5, B20 and B30 blends. As can be seen in this gure, all
Fig. 5. Variation of low heating value with biodiesel content.
Fig. 6. Variation of cloud point with biodiesel content.
2073
curves tend to intercept at a point which denes two zones
with dierent behaviour. Before the interception point
(approximately 80% distilled percentage), distillation tem-
perature increases with distilled percentage, while after this
point the trend is reversed. Fig. 8 shows the eect of biodie-
sel content on the distillation temperatures corresponding
to three representative distilled percentages: 10%, 50%
and 90%. These temperatures are designated as T10, T50
and T90, and the maximum values for these are commonly
specied in engine fuel quality standards. The ADDs
obtained using Kays mixing rule to estimate T10, T50
and T90 for the blends were 2.5%, 1.3% and 1.0%,
respectively.
3.3.6. Calculated cetane index
The cetane number is a basic property of diesel fuels that
indicates ignition characteristics. This parameter can be
measured in a specially designed test engine (ASTM
D613) or in a constant volume combustion apparatus
(ASTM D6890) [5,9]. However, these tests are awkward
and expensive. For this reason there have been many
attempts to develop methods to estimate the cetane number
of a fuel. In order to dierentiate predicted from measured
values, the former is called calculated cetane index (CCI),
and the latter cetane number [27]. The CCI can be deter-
mined using empirical correlations in accordance with the
ASTM D976 and D4737. Using ASTM D976, this param-
eter is obtained as a function of fuel density at 15 C and
the T50 distillation curve point. ASTM D4737 additionally
Fig. 7. Distillation curves of POB-D blends.
Fig. 8. Variation of distillation curve points wit biodiesel content.
2074 P. Benjumea et al. / Fuel 87 (2008) 20692075
Table 5
Calculated cetane indexes for pure fuels and B5 and B20 blends
ASTM standard Calculated cetane index
D B5 B20
D976 47.8 48.7 48.9
D4737 46.6 46.9 47.0
Fig. 9. Variation of calculated cetane index with biodiesel content.
takes into account T10 and T90 values. Table 5 shows the
CCI values using the two standards. Distillation curve
points were taken according to the measured values shown
in Fig. 7 and the values of density at 15 C were obtained
according to the linear regressions presented in Table 3.
For the blends tested (B5 and B20) the eect of biodiesel
content on the CCI of the blend was not signicant,
and the values obtained using both methods were similar.
For B100, the value of the CCI obtained using the ASTM
D4737 (CCI4737) was higher than that obtained using
the ASTM D976, and was in better agreement with the
measured cetane number reported for POB by Malaysian
Palm Oil Board researchers [28]. The better prediction
obtained using ASTM D4737 is most likely due to the
inclusion of the particular characteristics of the distillation
curve.
Two approaches were used to estimate the CCI4737 of
blends (see Fig. 9). In the rst, this parameter was calcu-
lated from values of blend densities at 15 C and distilla-
tion curve points obtained from Kays mixing rule. In the
second case, it was estimated directly from the mixing rule
as a function of biodiesel content and the value of the
parameter for pure fuels. As can be seen in Fig. 9, the
results obtained using both approaches are similar and
indicate that CCI increases with biodiesel content.
4. Conclusions
Basic properties of palm oil biodieseldiesel fuel blends
were measured according to ASTM standards.
Experimental data showing the variation of density and
kinematic viscosity with temperature were properly tted
by means of statistical regressions.
According to the low values obtained for the absolute
average deviations, it was found that simple mixing rules
are suitable for predicting the basic properties of palm oil
biodieseldiesel blends as a function of biodiesel content.
The variation of distillation temperature with distilled
B100 percentage for the tested blends is not uniform throughout
50.3 the boiling interval: there is an interception point (approx-
57.7 imately 80% distilled percentage) dividing two zones with
opposite behaviour.
The ASTM D4737 produces a calculated cetane index of
palm oil biodiesel in better agreement with the reported
cetane number than the corresponding to the ASTM
D976. This result is most likely due to the fact that the for-
mer standard takes into account the particular characteris-
tics of the distillation curve.
Acknowledgements
The authors wish to acknowledge the nancial support
of COLCIENCIAS (Instituto Colombiano para el Desarr-
ollo de la Ciencia y la Tecnologa Francisco Jose de Cal-
das) to the research project 1118-06-17327. They also
acknowledge the collaboration of ICP (Instituto Colombi-
ano del Petroleo).
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