Fuel 137 (2014) 2127

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Fuel
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Heat capacity measurements of pure fatty acid methyl esters

and biodiesels from 250 to 390 K
Jrme Pauly a,, Assamoi Cdric Kouakou a,b, Matthieu Habrioux a, Katell Le Mapihan b
a
Laboratoire des Fluides Complexes et leurs Rservoirs, UMR 5150, BP 1155, 64013 Pau Cedex, France
b
Total Rafnage Chimie, TRTGTOTAL Research & Technology Gonfreville, BP 27, 76700 Hareur, France

h i g h l i g h t s

 Heat capacities of FAME acid methyl esters were measured in both solid and liquid phases.
 Heat capacities of biodiesels were calculated through an ideal mixing rule.
 Experimental heat capacity of four biodiesels were then determined and compared.

a r t i c l e i n f o a b s t r a c t

Article history: The heat capacities at constant pressure of FAMEs were measured within the temperature range of
Received 20 May 2014 250390 K. The measurements were performed on 7 pure saturated fatty acid methyl esters and 5 unsat-
Received in revised form 9 July 2014 urated fatty acid methyl esters. These data were then employed to calculate heat capacities of four
Accepted 15 July 2014
different biodiesels (rapeseed and soybean origins) through an ideal mixing rule. The calculated and
Available online 2 August 2014
the experimental heat capacity of these biodiesels were then compared and an absolute average devia-
tion of 0.9% was observed.
Keywords:
2014 Elsevier Ltd. All rights reserved.
Fatty acid methyl ester
Heat capacity
Biodiesel

1. Introduction phase of several biodiesels were measured, and compared with the
data calculated from pure FAMEs values using an ideal mixing rule.
Biodiesel is an alternative renewable energy source dened by
the standard test method ASTM D2500 [1] as a fuel comprised of
2. Experimental
monoalkyl esters of long chain fatty acids derived from vegetable
oil, including used cooking oils, or animal fat. In order to describe
2.1. Chemicals
the behavior of the biodiesels under cold weather conditions
through multiphase thermodynamic models, thermophysical prop-
The pure compounds used in this work are either saturated or
erties of fatty acid methyl esters (FAMEs), such as heat capacity must
unsaturated FAMEs. Their purities, CAS registry numbers and ori-
be available for both liquid and solid phases. In this work, the heat
gins are listed in Table 1. They were purchased from SIGMA
capacities of various saturated and unsaturated pure FAMEs were
ALDRICH and used without further purication. For practical rea-
determined on a large range of temperature (250390 K) with a
sons, their name may be abbreviated in MeCn:m, where n corre-
highly sensitive micro differential scanning calorimeter. The exper-
sponds to the number of carbon atoms in the fatty acid chain
imental results were compared to the values found in the literature
before the ester group (COOMe); the second number m refers
[2]. This apparatus allowed the measurement of both liquid and
to the number of carbon-carbon double bonds in the hydrocar-
solid heat capacities in the same experiment. This point is truly
bonaceous moiety, also known as the FAME unsaturation degree.
signicant as it gives the possibility to accurately describe the solid
Two biodiesels respectively derived from soybean oil (BS) and
- liquid heat capacity change DC LS
p . The heat capacities of the liquid from rapeseed oil (BR) as well as two biodiesel blends (B1 and
B2) originated from the blend of various vegetable oils obtained
from DIESTER company (France) were analyzed. Their FAMEs con-
Corresponding author. Tel.: +33 5 59 40 76 91; fax: +33 5 59 40 76 95. tent was analyzed by the laboratory ITERG (France) which is certi-
E-mail address: jerome.pauly@univ-pau.fr (J. Pauly). ed in fats and oils analysis by the French state. The compositions

http://dx.doi.org/10.1016/j.fuel.2014.07.037
0016-2361/ 2014 Elsevier Ltd. All rights reserved.
22 J. Pauly et al. / Fuel 137 (2014) 2127

Table 1
List of the studied saturated and unsaturated pure FAMEs.

Name Abbreviation CAS RN Mass fraction (%) Origin

Methyl decanoate MeC10:0 110-42-9 99.0 Sigma Aldrich
Methyl laurate MeC12:0 111-82-0 99.5 Sigma Aldrich
Methyl myristate MeC14:0 124-10-7 99.0 Sigma Aldrich
Methyl palmitate MeC16:0 112-39-0 99.0 Sigma Aldrich
Methyl stearate MeC18:0 112-61-8 99.5 Sigma Aldrich
Methyl oleate MeC18:1 112-62-9 99.0 Sigma Aldrich
Methyl linoleate MeC18:2 112-63-0 99.0 Sigma Aldrich
Methyl linolenate MeC18:3 301-00-8 99.0 Sigma Aldrich
Methyl arachidate MeC20:0 1120-28-1 99.0 Sigma Aldrich
Methyl cis-11-eicosenoate MeC20:1 2390-09-2 98.0 Sigma Aldrich
Methyl behenate MeC22:0 929-77-1 99.0 Sigma Aldrich
Methyl cis-13-docosenoate MeC22:1 120-34-9 99.0 Sigma Aldrich

were obtained by gas chromatography according to the standard
test method EN 14103. The FAMEs of which the concentrations
were higher than 0.1 wt% are reported in Table 2. Rapeseed oil
was the major vegetable source used to produce the biodiesel
blends B1 and B2, while the quantities of the two other feedstocks
(soybean and palm oil) were limited in accordance with the Euro-
pean transportation fuel specications [3]. The rst reason for
these limitations was because palm oil transesterication leads
mainly to linear saturated FAMEs which can nucleate and form
crystals at positive temperatures above freezing. The second was
that soybean oil transesterication produces biodiesel rich in
polyunsaturated compounds which are responsible for poor oxida-
tive stability [4,5]. All the chemicals were stored at 4 C to avoid
potential degradations at warmer temperatures.
2.2. Micro Differential Scanning Calorimetry (lDSC)
The heat capacities were measured by using the SETARAM
Micro DSC VII Evo differential scanning calorimeter [6]. This appa-
ratus is equipped with an external cooling uid (water) around a
calorimetric block allowing a range of temperature going from
228.15 to 393.15 K. The temperature regulation is ensured by
two stages of high sensitivity Peltier thermo elements located
around the measuring and the reference cells, and on the calori-
metric block. This arrangement guarantees low inertia, accurate
temperature control and high output signal sensitivity. The atmo-
sphere inside the calorimetric block is dried with nitrogen gas (vol-
ume purity P 99.995%).
This calorimeter is based on Calverts principle and the output
signal is given by the difference of the heat ux received by the
ux meters which completely surround both the reference and
measuring cells. Temperature and caloric calibrations were per-
formed according the procedures recommended by the manufactur-
er by means of Joule effect method. The performance of the
calorimeter was revaluated every two months. The output data,
the differential heat ux (0.005 mW) and the temperature
(0.01 K) versus time were monitored and analyzed by the Calisto
SETARAM software package, respectively Data Acquisition and AKTS
Processing v1.088.
2.3. Experimental procedure
For all measurements the SETARAM cylindrical standard batch
vessels (Fig. 1) were used. They are made of Hastelloy C276 and
have a volume of 1 cm3 (6.4 mm internal diameter, 19.5 mm of
useful height). A sample mass of 0.5 g (0.0001) g were weighed
with an OHAUS Explorer E0RR80 balance.
The experimental procedure started with a pretreatment in
which the sample was cooled to 243.15 K and kept at this temper-
ature during one hour. Then the heat capacity measurements in
solid and liquid state were carried out using the scanning or con-
tinuous method with a constant heating rate of 0.2 K min1 as
already used with this kind of apparatus [7,8]. Different tests were
performed with diverse scanning rate from 0.01 to 1 K min1.
Using a very slow heating rate can cause important background
noise due to the sensitivity of the apparatus. On the contrary a
too high heating rate might generate a decay between the temper-
ature inside the calorimetric block and the cell temperature. The
selected scanning rate was the best compromise between main-
taining a weak thermal lag in the temperature and heat ux mea-
surements and minimize heat accumulation effect in the sample.
This method needed a set of three different experiments. The three

Table 2
Composition (mass%) of the biodiesel blend studied.

FAMEs content (mass%)

Rapeseed Biodiesel (BR) Soybean Biodiesel (BS) Biodiesel blend (B1) Biodiesel blend (B2)
MeC12:0 0.1 0.1 0.1 0.1
MeC14:0 0.1 0.1 0.2 0.1
MeC16:0 4.9 10.5 9.6 6.5
MeC16:1 0.3 0.2 0.2 0.2
MeC18:0 1.5 4.5 2.2 2.0
MeC18:1 60.3 23.5 56.3 57.5
MeC18:2 19.2 51.3 20.1 22.6
MeC18:3 10.2 7.5 8.4 8.2
MeC20:0 0.5 0.4 0.5 0.5
MeC20:1 1.3 0.3 1.1 1.1
MeC22:0 0.3 0.4 0.3 0.3
MeC22:1 0.3 _ 0.2 0.2
MeC24:0 0.1 0.2 0.1 0.1
Other FAMEs 0.4 0.3 _ 0.3
Non identied 0.5 0.7 0.7 0.3
 J. Pauly et al. / Fuel 137 (2014) 2127 23

was lled with n-decane (molar purity P 99.0%). N-decane was

selected as a reference due to its well-known isobaric heat capacity
[9,10] and that the measured differential heat ux of this substance
a was clearly higher than those of the FAMEs as shown by Fig. 2. Both
b experiments (I) and (II) ensure a proper caloric correction for all
c the studied species and were performed only once before the
beginning of a set of experiments on FAME samples. After that,
d
the experiment (III) was carried out for each sample which lled
the measuring vessel whereas the reference vessel left empty. In
Fig. 2 the gap in the heat ow curve in run III corresponds to the
melting peak of the component. This measurement was repeated
twice for each sample. The three experiments were then used to
e calculate the isobaric heat capacity from the following expression:
HF S  HF E mR
CpS   CpR 1
HF R  HF E mS
where HF stands for the differential heat ux between the two ves-
sels, m for the uid mass and Cp for the isobaric heat capacity. The
subscripts E, R and S refer respectively to empty (experiment I), ref-
erence material (experiment II) and sample (experiment III).

3. Uncertainty measurement and calibration method

f
g
h FAMEs were below 10 kPa at all experimental temperatures and
Fig. 1. Illustration of SETARAM cylindrical standard batch vessel: (a) temperature
regulation chamber using an external cooling uid, (b) intermediate temperature
regulation chamber using Peltier thermo-elements, (c) calorimetric measurement
compartment, (d) Peltier thermo-elements, (e) external cooling uid, (f) sample
vessel, (g) heat ux transducers and (h) reference vessel.
corresponding heat ows are presented in Fig. 2. Experiment (I)
was performed with both the reference and measuring vessels
empty in order to obtain the heat ux base line. In experiment
(II), the reference vessel was let empty and the measuring vessel
The rst potential source of error for the heat capacity measure-
ments was the free vapor volume in the cell during the experiment.
In the measurement procedure more than 70% of the inner cell was
occupied by the sample. The vapor pressures of all the studied
their normal boiling point were more than 100 K higher than the
maximum studied temperature [11,12]. In these conditions, it
was thus not necessary to apply any correction related to the sam-
ple vaporization as observed by various authors [10,13,14]. Others
factors like the temperature, the differential heat ux, the sample
weight and the heat capacity of the reference uid (n-decane) also
affects the heat capacity results. Their expanded uncertainties with
a level of condence of 0.95 (k = 2) was respectively 0.01 K and
0.005 mW from calorimeter manufacturer estimation, 0.0001 g
from balance manufacturer and 0.3% from 247 to 314 K, 0.5% from
314 to 462 K [10]. All these contributions were taken into account
and reported in the heat capacity uncertainty by using a quadratic
propagation law. The combined expanded uncertainty with a level

2 400
EXO

1 380

0 360

-1 340
Temperature (K)
Healow (mW)

-2 320

-3 300

-4 280

-5 260

-6 240
0 2 4 6 8 10 12
Time (hours)

Fig. 2. Heat ux and temperature output data versus time from experiments (I-III); ( ) temperature heating program versus time, ( ) experiment (I): both empty
vessels, ( ) experiment (II): empty reference vessel and reference material, () experiment (III): empty reference vessel and sample MeC10:0.
24 J. Pauly et al. / Fuel 137 (2014) 2127

of condence 0.95 (k = 2) of this heat capacity measurement 4. Results

method was estimated as 0.5%.
The calibration approach was checked by measuring the heat 4.1. Pure components
capacity of the n-dodecane (molar purity P 99.0%) in the liquid
state. The absolute average deviation (Eq. (2)) was about 0.40% The melting point (Table 3) of the majority of the pure compo-
compared to the data obtained by the NIST [9] or by Zbransky nents was previously measured at atmospheric pressure by using
et al. [10]. In the solid state, the results were checked by measuring the lDSC calorimeter and by optical microscopy for which the
the heat capacity of the n-hexadecane (molar purity P 99.0%). The experimental technique was described by Kouakou et al. [16]. In
AAD was about 1.1% compared to the data measured by Messerly this work to complete our set of data, the same method was used
et al. [15] from 250 to 273 K. The accuracy uncertainty of Messerly to measure the melting points of the MeC22:0, MeC20:1 and the
et al. does not exceed 0.2% except in regions near phase transitions MeC22:1 (Table 3). The melting points were determined with an
where their data are less precise and less accurate. As for Fatty acid accuracy of 0.2 K applying the microscope technique and 0.1 K
methyl esters we noticed an abnormal increase of the heat capac- through the lDSC technique. The discrepancy between the mea-
ities below the melting point. This effect has been already reported sured temperatures from this work and the ones available in the
by other researcher and seems to have different level of impor- literature can have several explanations as described in previous
tance in function of the experimental procedure. It is one of the work by Kouakou et al. [16]. All these melting points constitute
reason why we have ADD of 1% in this region and 0.2% far from important information before the measurements of heat capacities
the melting point. This phenomenon has been called prerotation as they allow distinguishing the liquid phase from the solid phase.
and corresponds to the beginning of the rotation of the molecules Concerning the melting temperatures of MeC18:2 and the
around their long axes. MeC18:3 it was for us impossible to used our experimental device
All these measurements were performed in duplicate and the as the values are out of the measuring range of our technique.
isobaric heat capacity repeatability was about 0.2%. We used the scanning method to obtain the thermogram of the
X fatty acid methyl esters (Fig. 2) leading, after data processing, to
n
jCpexp  Cpcalc j
i i
AAD 2 the experimental heat capacity of FAMEs. Thus the experimental
i1
Cpexp
i heat capacities of twelve pure FAMEs with different degrees of
unsaturation over a large range of temperature 250390 K were
tted with a second order polynomial equation Cp = f(T). The stan-
dard deviations do not exceed 0.3% for each pure component in
Table 3 both solid and liquid phases.
Melting temperatures at atmospheric pressure measured previously [16] and in this
Liquid molar heat capacities for the saturated fatty acid methyl
work by lDSC (Tm1) by microscopy (Tm2) and the ones found in the literature (Tref).
esters as a function of temperature are presented in Table 4 and
FAME compounds Tm1 (K) Tm2 (K) Tref (K) shown in Fig. 3. For each component, the rst data is taken at a
MeC10:0 260.1d 260.05d 260.3a temperature approximately 10 K higher than the melting point of
MeC12:0 278.2d 278.45d 278.2a the component to be reasonably far from the melting peak. In
MeC14:0 291.8d 291.55d 292.1a the same way, the solid molar heat capacities for the saturated
MeC16:0 302.9d 301.95d 302.7a
MeC18:0 311.6d 311.55d 311.8a
FAMEs as a function of temperature are presented in Table 5 and
MeC18:1 253.6d 253.45d 253.0b shown in Fig. 3. As for liquid phase, the highest value is given
MeC18:2 235.4b around 5 or 10 K colder than the melting point.
MeC18:3 227.7c The liquid molar heat capacities increase with the temperature
MeC20:0 319.8d 319.45d 319.5a
but also with the number of carbon atoms before the ester group
MeC20:1 267.2e 265.4b
MeC22:0 325.7e 325.55e 326.4b (Fig. 3). However, in the case of saturated FAMEs, the length of
MeC22:1 272.6e 270.1b the molecule does not seem to affect the slope value of the heat
a
capacity versus the temperature. The same conclusion can be
Van Bommel et al. [2].
b
Knothe et al. [17]. drawn from the solid heat capacity in Fig. 3 but it has to be noticed
c
Handbook of Chemistry and Physics [18]. that the slope of the curve is higher for the solid phase than for the
d
Kouakou et al. [16]. liquid as shown in Fig. 3. This more pronounced increase of heat
e
This work. capacity of FAMEs with temperature in the solid phase can be due
to a regular onset of molecular rotational freedom corresponding

Table 4
Liquid molar heat capacity of saturated of fatty acid methyl esters as a function of temperature.

T (K) Liquid molar heat capacity (J mol1 K1)

MeC10:0 MeC12:0 MeC14:0 MeC16:0 MeC18:0 MeC20:0 MeC22:0
270 367.25
280 369.64
290 372.57 427.57
300 376.05 434.22 494.59
310 380.08 440.94 501.77 569.49
320 384.66 447.72 508.89 575.75 643.90
330 389.79 454.57 515.95 582.16 650.59 713.29
340 395.46 461.48 522.95 588.71 657.23 723.36 790.85
350 401.69 468.46 529.90 595.39 663.81 733.23 800.69
360 408.46 475.51 536.79 602.22 670.34 742.92 810.30
370 415.78 482.62 543.62 609.19 676.82 752.42 819.68
380 423.65 489.80 550.39 616.30 683.24 761.73 828.82
390 432.06 497.04 557.11 623.55 689.60 770.85 837.72
 J. Pauly et al. / Fuel 137 (2014) 2127 25

2.00
790
1.50

690 1.00
Cp (J.mol -1 .K -1 )

[Cpexp -Cplit)/C plit]*100

0.50
590
0.00
490
-0.50

390 -1.00

-1.50
290
240 260 280 300 320 340 360 380 400
-2.00
T (K) 270 280 290 300 310 320 330 340 350
MeC10:0 MeC12:0 MeC14:0 MeC16:0 MeC18:0 MeC20:0 MeC22:0
T (K)
MeC10:0 MeC12:0 MeC14:0 MeC16:0 MeC18:0 MeC20:0
Fig. 3. Molar heat capacity versus temperature for saturated FAMEs in both solid
and liquid phases. Fig. 4a. Relative deviations for liquid molar heat capacities of FAMEs with the
literature [2].

to the rotation of the molecule about their main axis. Moreover the
step change between the liquid heat capacity and the correspond-
5.00
ing solid is classically attributed to the higher degree of freedom
for vibrations of molecule in liquid state and to the energy
0.00
employed for overcoming of the Van der Waals attractive forces.

[Cpexp -Cplit)/C plit]*100

Due to the important lack of experimental data for saturated
-5.00
fatty acid methyl esters, our experimental data were only com-
pared to those reported by Van Bommel et al. [2] except for
-10.00
MeC22:0 for which no data were available. It is important to spec-
ify that Van Bommel et al. [2] did not report uncertainties in his
-15.00
work.
For the liquid phase, our results are consistent with those of the
-20.00
literature, showing a maximum deviation of 1.7% and an absolute
average deviation of 0.34% as presented in Fig. 4a. For the solid
part, the relative deviations with the only data available in the lit- -25.00
250 260 270 280 290 300 310
erature show a maximum of 22% whereas the AAD is 2.57% T (K)
(Fig. 4b).
MeC10:0 MeC12:0 MeC14:0 MeC16:0 MeC18:0 MeC20:0
Some explanations have to be given in order to understand
those deviations in the solid phase. In Fig. 4b, we easily notice that Fig. 4b. Relative deviations for solid molar heat capacities of FAMEs with the
the maximum deviations are always obtained for the highest tem- literature [2].

perature. The measurements of solid and liquid molar heat capac-

ity of the MeC18:0 are gathered in Fig. 5, the star symbols and the
dashed lines representing respectively our experimental data and
those of Van Bommel et al. Fig. 5 clearly shows that some data from
Van Bommel et al. seem to be already on the melting peak of the
pure compound. Therefore without this point the AAD drops to
1.27% and the maximum relative deviation is about 4% for the solid
molar heat capacity. There are some possible explanations for the
difference observed closed to the melting point. One being that
the experimental technique and procedure are not the same while
Van Bommel et al. used an adiabatic calorimeter with a different
heating of the system step by step. The second one being that
premelting of impurities can play a role since the chemicals were
not provided by the same manufacturer. The third one corresponds

Table 5
Solid molar heat capacity of saturated of fatty acid methyl esters as a function of temperature.

T (K) Solid molar heat capacity (J mol1 K1)

MeC10:0 MeC12:0 MeC14:0 MeC16:0 MeC18:0 MeC20:0 MeC22:0
250 301.44 324.05 359.10 390.73 436.83 474.70 517.47
255 329.96 361.82 396.56 445.52 482.14 525.65
260 337.33 366.69 403.44 454.63 490.31 534.66
265 346.14 373.71 411.35 464.17 499.21 544.51
270 356.40 382.88 420.30 474.14 508.85 555.19
275 394.20 430.28 484.54 519.21 566.71
280 407.67 441.30 495.37 530.31 579.06
285 453.36 506.62 542.14 592.25
290 466.46 518.31 554.70 606.27
295 480.60 530.42 568.00 621.12
300 542.97 582.02 636.81
305 555.94 596.78 653.33
310 612.26 670.68
315 688.87
320 707.89
26 J. Pauly et al. / Fuel 137 (2014) 2127

840
790
790
690
740
Cp ( J.mol-1 .K -1 )

Cp ( J.mol -1 .K -1 )
590
690

490
640

390 590

290 540
240 260 280 300 320 340 360 380 400 260 280 300 320 340 360 380 400
T (K) T (K)
Our work Melng point van Bommel et al. MeC18:0 MeC18:1 MeC18:2 MeC18:3 MeC20:0 MeC20:1 MeC22:0 MeC22.1

Fig. 5. Molar heat capacities versus temperature of the methyl stearate (MeC18:0). Fig. 6. Liquid molar heat capacity versus temperature for unsaturated FAMEs and
comparison with their degree of unsaturation.

to the beginning of the rotation of the molecules around their long

axes as already mentioned in this work.
2.2
The molar heat capacities of the unsaturated pure FAMEs are
separately presented as these components do not exhibit melting 2.15
point in the range of temperature corresponding to our study. The
2.1
values are then reported in Table 6 but they cannot be compared
as no data on large range of temperature are available in the litera- Cp (J.g-1 .K -1 ) 2.05
ture for these pure components. Even if the results are closed, the
heat capacity of unsaturated FAMEs decreases with the degree of 2
Calculaon
unsaturation as shown in Fig. 6. The heat capacity trend for unsat- 1.95 Experimental
urated esters does not show a sharp deviation from the trend of the
saturated esters. But if we consider a constant temperature value, a 1.9
nonlinear decrease of the heat capacity is observed as the number
1.85
of double bonds in the molecule increases. A completely different
curve was observed as the degree of unsaturation progressed lead- 1.8
290 300 310 320 330 340 350 360 370
ing to 5.11% difference between the MeC18:0 and MeC18:1 (based
T (K)
on MeC18:0), 1.16% difference between MeC18:1 and MeC18:2
(based on MeC18:1), and a 1.11% difference between MeC18:2 Fig. 7a. Liquid mass heat capacity versus temperature for Rapeseed Biodiesel (BR).
and MeC18:3 (based on MeC18:2).

2.2
4.2. Biodiesel systems
2.15
To quantify the effect of variations in oil composition on the
2.1
heat capacity prediction, we have tested biodiesels derived from
rapeseed oil, soybean oil and other from various oils with FAMEs 2.05
Cp (J.g-1 .K -1 )

compositions close to those of the rapeseed biodiesel. Considering

biodiesel blend as a nearly ideal system [11], a classical mixing rule 2
Calculaon
was applied to determine the liquid heat capacity of a real mixture 1.95 Experimental
by using the heat capacity of each pure FAME. We used an
1.9

1.85
Table 6
Liquid molar heat capacity of unsaturated of fatty acid methyl esters as a function of 1.8
290 300 310 320 330 340 350 360 370
temperature.
T (K)
T (K) Liquid molar heat capacity (J mol1 K1)
Fig. 7b. Liquid mass heat capacity versus temperature for Soybean Biodiesel (BS).
MeC18:1 MeC18:2 MeC18:3 MeC20:1 MeC22.1
270 564.63 556.95 552.78 617.11
280 572.02 564.95 560.71 629.04 698.76
290 579.76 573.10 568.69 640.45 707.34 arithmetic mole or weight fraction average of the pure component
300 587.84 581.43 576.74 651.34 716.25 values even though it neglects any contribution due to enthalpy of
310 596.27 589.92 584.85 661.71 725.50 mixing.
320 605.05 598.58 593.02 671.57 735.08 Measurements have been made in range of temperature from
330 614.18 607.41 601.25 680.91 744.99
340 623.65 616.40 609.54 689.73 755.24
300 to 360 K. The results for the four different investigated systems
350 633.47 625.56 617.89 698.04 765.83 are given in Figs. 7a7d. They show a comparison between the
360 643.64 634.88 626.30 705.83 776.74 experimental mass heat capacity of the biodiesel and the results
370 654.15 644.37 634.77 713.10 787.99 from calculation with the arithmetic mixing rule. The slopes of
380 665.01 654.03 643.30 719.85 799.58
the curve are correctly described for all the systems as the small
390 676.22 663.85 651.89 726.09 811.50
deviations in Figs. 7a and 7c can be assigned to experimental
 J. Pauly et al. / Fuel 137 (2014) 2127 27

2.2 Biodiesels have to be considered as complex mixtures but actually

the compositions of these systems are mainly driven by a triplet of
2.15
fatty acid methyl ester decreasing the asymmetric characteristic of
2.1 the blends.

2.05
Cp (J.g-1 .K -1 )

5. Conclusion
2
Calculaon
The main goal of this work was to investigate the effect of the
1.95 Experimental
temperature (250390 K) on the heat capacities of various saturated
1.9 and unsaturated fatty acid methyl esters. The large range of temper-
ature studied allowed analyze this thermophysical property in both
1.85
liquid and solid states. The data were compared with the unique
1.8 experimental data from the literature for saturated FAMEs whereas
290 300 310 320 330 340 350 360 370
the values for unsaturated FAMEs constitute a new contribution.
T (K)
The heat capacities at constant pressure for different biodiesels
Fig. 7c. Liquid mass heat capacity versus temperature for biodiesel blend 1 (B1). were obtained by the same procedure. The comparison of our
results with the calculated values has shown that the use of an ide-
2.2
al mixing rule can be considered as a reasonable rst approxima-
tion to estimate this thermodynamic property.
2.15
References
2.1

2.05
[1] ASTM Standard D2500-11. Standard test method for cloud point of petroleum
Cp (J.g-1 .K-1 )

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