Fuel 137 (2014) 2127

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Fuel
journal homepage: www.elsevier.com/locate/fuel

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
b

Laboratoire des Fluides Complexes et leurs Rservoirs, UMR 5150, BP 1155, 64013 Pau Cedex, France
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

Article history:
Received 20 May 2014
Received in revised form 9 July 2014
Accepted 15 July 2014
Available online 2 August 2014
Keywords:
Fatty acid methyl ester
Heat capacity
Biodiesel

a b s t r a c t
The heat capacities at constant pressure of FAMEs were measured within the temperature range of
250390 K. The measurements were performed on 7 pure saturated fatty acid methyl esters and 5 unsaturated fatty acid methyl esters. These data were then employed to calculate heat capacities of four
different biodiesels (rapeseed and soybean origins) through an ideal mixing rule. The calculated and
the experimental heat capacity of these biodiesels were then compared and an absolute average deviation of 0.9% was observed.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Biodiesel is an alternative renewable energy source dened by
the standard test method ASTM D2500 [1] as a fuel comprised of
monoalkyl esters of long chain fatty acids derived from vegetable
oil, including used cooking oils, or animal fat. In order to describe
the behavior of the biodiesels under cold weather conditions
through multiphase thermodynamic models, thermophysical properties of fatty acid methyl esters (FAMEs), such as heat capacity must
be available for both liquid and solid phases. In this work, the heat
capacities of various saturated and unsaturated pure FAMEs were
determined on a large range of temperature (250390 K) with a
highly sensitive micro differential scanning calorimeter. The experimental results were compared to the values found in the literature
[2]. This apparatus allowed the measurement of both liquid and
solid heat capacities in the same experiment. This point is truly
signicant as it gives the possibility to accurately describe the solid
- liquid heat capacity change DC LS
p . The heat capacities of the liquid

Corresponding author. Tel.: +33 5 59 40 76 91; fax: +33 5 59 40 76 95.

E-mail address: jerome.pauly@univ-pau.fr (J. Pauly).
http://dx.doi.org/10.1016/j.fuel.2014.07.037
0016-2361/ 2014 Elsevier Ltd. All rights reserved.

phase of several biodiesels were measured, and compared with the

data calculated from pure FAMEs values using an ideal mixing rule.
2. Experimental
2.1. Chemicals
The pure compounds used in this work are either saturated or
unsaturated FAMEs. Their purities, CAS registry numbers and origins are listed in Table 1. They were purchased from SIGMA
ALDRICH and used without further purication. For practical reasons, their name may be abbreviated in MeCn:m, where n corresponds to the number of carbon atoms in the fatty acid chain
before the ester group (COOMe); the second number m refers
to the number of carbon-carbon double bonds in the hydrocarbonaceous moiety, also known as the FAME unsaturation degree.
Two biodiesels respectively derived from soybean oil (BS) and
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 content was analyzed by the laboratory ITERG (France) which is certied in fats and oils analysis by the French state. The compositions

22

J. Pauly et al. / Fuel 137 (2014) 2127

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

decanoate
laurate
myristate
palmitate
stearate
oleate
linoleate
linolenate
arachidate
cis-11-eicosenoate
behenate
cis-13-docosenoate

Abbreviation

CAS RN

Mass fraction (%)

Origin

MeC10:0
MeC12:0
MeC14:0
MeC16:0
MeC18:0
MeC18:1
MeC18:2
MeC18:3
MeC20:0
MeC20:1
MeC22:0
MeC22:1

110-42-9
111-82-0
124-10-7
112-39-0
112-61-8
112-62-9
112-63-0
301-00-8
1120-28-1
2390-09-2
929-77-1
120-34-9

99.0
99.5
99.0
99.0
99.5
99.0
99.0
99.0
99.0
98.0
99.0
99.0

Sigma
Sigma
Sigma
Sigma
Sigma
Sigma
Sigma
Sigma
Sigma
Sigma
Sigma
Sigma

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 European 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 oxidative 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 apparatus 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 calorimetric block. This arrangement guarantees low inertia, accurate
temperature control and high output signal sensitivity. The atmosphere inside the calorimetric block is dried with nitrogen gas (volume 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

Aldrich
Aldrich
Aldrich
Aldrich
Aldrich
Aldrich
Aldrich
Aldrich
Aldrich
Aldrich
Aldrich
Aldrich

measuring cells. Temperature and caloric calibrations were performed according the procedures recommended by the manufacturer 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 temperature during one hour. Then the heat capacity measurements in
solid and liquid state were carried out using the scanning or continuous 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 temperature inside the calorimetric block and the cell temperature. The
selected scanning rate was the best compromise between maintaining a weak thermal lag in the temperature and heat ux measurements 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%)

MeC12:0
MeC14:0
MeC16:0
MeC16:1
MeC18:0
MeC18:1
MeC18:2
MeC18:3
MeC20:0
MeC20:1
MeC22:0
MeC22:1
MeC24:0
Other FAMEs
Non identied

Rapeseed Biodiesel (BR)

Soybean Biodiesel (BS)

Biodiesel blend (B1)

Biodiesel blend (B2)

0.1
0.1
4.9
0.3
1.5
60.3
19.2
10.2
0.5
1.3
0.3
0.3
0.1
0.4
0.5

0.1
0.1
10.5
0.2
4.5
23.5
51.3
7.5
0.4
0.3
0.4
_
0.2
0.3
0.7

0.1
0.2
9.6
0.2
2.2
56.3
20.1
8.4
0.5
1.1
0.3
0.2
0.1
_
0.7

0.1
0.1
6.5
0.2
2.0
57.5
22.6
8.2
0.5
1.1
0.3
0.2
0.1
0.3
0.3

23

J. Pauly et al. / Fuel 137 (2014) 2127

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
was clearly higher than those of the FAMEs as shown by Fig. 2. Both
experiments (I) and (II) ensure a proper caloric correction for all
the studied species and were performed only once before the
beginning of a set of experiments on FAME samples. After that,
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
calculate the isobaric heat capacity from the following expression:

a
b
c
d

CpS

HF S  HF E mR

 CpR
HF R  HF E mS

where HF stands for the differential heat ux between the two vessels, m for the uid mass and Cp for the isobaric heat capacity. The
subscripts E, R and S refer respectively to empty (experiment I), reference material (experiment II) and sample (experiment III).
3. Uncertainty measurement and calibration method
f

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 measurements 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
FAMEs were below 10 kPa at all experimental temperatures and
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 sample 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

400

380

360

-1

340

-2

320

-3

300

-4

280

-5

260

-6

10

12

Temperature (K)

Healow (mW)

EXO

240

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

method was estimated as 0.5%.
The calibration approach was checked by measuring the heat
capacity of the n-dodecane (molar purity P 99.0%) in the liquid
state. The absolute average deviation (Eq. (2)) was about 0.40%
compared to the data obtained by the NIST [9] or by Zbransky
et al. [10]. In the solid state, the results were checked by measuring
the heat capacity of the n-hexadecane (molar purity P 99.0%). The
AAD was about 1.1% compared to the data measured by Messerly
et al. [15] from 250 to 273 K. The accuracy uncertainty of Messerly
et al. does not exceed 0.2% except in regions near phase transitions
where their data are less precise and less accurate. As for Fatty acid
methyl esters we noticed an abnormal increase of the heat capacities below the melting point. This effect has been already reported
by other researcher and seems to have different level of importance in function of the experimental procedure. It is one of the
reason why we have ADD of 1% in this region and 0.2% far from
the melting point. This phenomenon has been called prerotation
and corresponds to the beginning of the rotation of the molecules
around their long axes.
All these measurements were performed in duplicate and the
isobaric heat capacity repeatability was about 0.2%.

AAD

n
X
jCpexp  Cpcalc j
i

i1

Cpexp
i

Table 3
Melting temperatures at atmospheric pressure measured previously [16] and in this
work by lDSC (Tm1) by microscopy (Tm2) and the ones found in the literature (Tref).

a
b
c
d
e

FAME compounds

Tm1 (K)

Tm2 (K)

Tref (K)

MeC10:0
MeC12:0
MeC14:0
MeC16:0
MeC18:0
MeC18:1
MeC18:2
MeC18:3
MeC20:0
MeC20:1
MeC22:0
MeC22:1

260.1d
278.2d
291.8d
302.9d
311.6d
253.6d

260.05d
278.45d
291.55d
301.95d
311.55d
253.45d

319.8d
267.2e
325.7e
272.6e

319.45d

260.3a
278.2a
292.1a
302.7a
311.8a
253.0b
235.4b
227.7c
319.5a
265.4b
326.4b
270.1b

325.55e

Van Bommel et al. [2].

Knothe et al. [17].
Handbook of Chemistry and Physics [18].
Kouakou et al. [16].
This work.

4. Results
4.1. Pure components
The melting point (Table 3) of the majority of the pure components was previously measured at atmospheric pressure by using
the lDSC calorimeter and by optical microscopy for which the
experimental technique was described by Kouakou et al. [16]. In
this work to complete our set of data, the same method was used
to measure the melting points of the MeC22:0, MeC20:1 and the
MeC22:1 (Table 3). The melting points were determined with an
accuracy of 0.2 K applying the microscope technique and 0.1 K
through the lDSC technique. The discrepancy between the measured temperatures from this work and the ones available in the
literature can have several explanations as described in previous
work by Kouakou et al. [16]. All these melting points constitute
important information before the measurements of heat capacities
as they allow distinguishing the liquid phase from the solid phase.
Concerning the melting temperatures of MeC18:2 and the
MeC18:3 it was for us impossible to used our experimental device
as the values are out of the measuring range of our technique.
We used the scanning method to obtain the thermogram of the
fatty acid methyl esters (Fig. 2) leading, after data processing, to
the experimental heat capacity of FAMEs. Thus the experimental
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 standard deviations do not exceed 0.3% for each pure component in
both solid and liquid phases.
Liquid molar heat capacities for the saturated fatty acid methyl
esters as a function of temperature are presented in Table 4 and
shown in Fig. 3. For each component, the rst data is taken at a
temperature approximately 10 K higher than the melting point of
the component to be reasonably far from the melting peak. In
the same way, the solid molar heat capacities for the saturated
FAMEs as a function of temperature are presented in Table 5 and
shown in Fig. 3. As for liquid phase, the highest value is given
around 5 or 10 K colder than the melting point.
The liquid molar heat capacities increase with the temperature
but also with the number of carbon atoms before the ester group
(Fig. 3). However, in the case of saturated FAMEs, the length of
the molecule does not seem to affect the slope value of the heat
capacity versus the temperature. The same conclusion can be
drawn from the solid heat capacity in Fig. 3 but it has to be noticed
that the slope of the curve is higher for the solid phase than for the
liquid as shown in Fig. 3. This more pronounced increase of heat
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)

270
280
290
300
310
320
330
340
350
360
370
380
390

Liquid molar heat capacity (J mol1 K1)

MeC10:0

MeC12:0

MeC14:0

MeC16:0

MeC18:0

MeC20:0

MeC22:0

367.25
369.64
372.57
376.05
380.08
384.66
389.79
395.46
401.69
408.46
415.78
423.65
432.06

427.57
434.22
440.94
447.72
454.57
461.48
468.46
475.51
482.62
489.80
497.04

494.59
501.77
508.89
515.95
522.95
529.90
536.79
543.62
550.39
557.11

569.49
575.75
582.16
588.71
595.39
602.22
609.19
616.30
623.55

643.90
650.59
657.23
663.81
670.34
676.82
683.24
689.60

713.29
723.36
733.23
742.92
752.42
761.73
770.85

790.85
800.69
810.30
819.68
828.82
837.72

25

J. Pauly et al. / Fuel 137 (2014) 2127

2.00
1.50

690

[Cpexp -Cplit)/C plit]*100

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

790

590
490
390
290
240

1.00
0.50
0.00
-0.50
-1.00
-1.50

260

280

300

320

340

360

380

400

-2.00
270

T (K)
MeC12:0

MeC14:0

MeC16:0

MeC18:0

MeC20:0

280

290

300

MeC22:0

Fig. 3. Molar heat capacity versus temperature for saturated FAMEs in both solid
and liquid phases.

to the rotation of the molecule about their main axis. Moreover the
step change between the liquid heat capacity and the corresponding solid is classically attributed to the higher degree of freedom
for vibrations of molecule in liquid state and to the energy
employed for overcoming of the Van der Waals attractive forces.
Due to the important lack of experimental data for saturated
fatty acid methyl esters, our experimental data were only compared to those reported by Van Bommel et al. [2] except for
MeC22:0 for which no data were available. It is important to specify that Van Bommel et al. [2] did not report uncertainties in his
work.
For the liquid phase, our results are consistent with those of the
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 literature show a maximum of 22% whereas the AAD is 2.57%
(Fig. 4b).
Some explanations have to be given in order to understand
those deviations in the solid phase. In Fig. 4b, we easily notice that
the maximum deviations are always obtained for the highest temperature. The measurements of solid and liquid molar heat capacity 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

310

320

330

340

350

T (K)
MeC10:0

MeC12:0

MeC14:0

MeC16:0

MeC18:0

MeC20:0

Fig. 4a. Relative deviations for liquid molar heat capacities of FAMEs with the
literature [2].

5.00
0.00

[Cpexp -Cplit)/C plit]*100

MeC10:0

-5.00
-10.00
-15.00
-20.00
-25.00
250

260

270

280

290

300

310

T (K)
MeC10:0

MeC12:0

MeC14:0

MeC16:0

MeC18:0

MeC20:0

Fig. 4b. Relative deviations for solid molar heat capacities of FAMEs with the
literature [2].

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)

250
255
260
265
270
275
280
285
290
295
300
305
310
315
320

Solid molar heat capacity (J mol1 K1)

MeC10:0

MeC12:0

MeC14:0

MeC16:0

MeC18:0

MeC20:0

MeC22:0

301.44

324.05
329.96
337.33
346.14
356.40

359.10
361.82
366.69
373.71
382.88
394.20
407.67

390.73
396.56
403.44
411.35
420.30
430.28
441.30
453.36
466.46
480.60

436.83
445.52
454.63
464.17
474.14
484.54
495.37
506.62
518.31
530.42
542.97
555.94

474.70
482.14
490.31
499.21
508.85
519.21
530.31
542.14
554.70
568.00
582.02
596.78
612.26

517.47
525.65
534.66
544.51
555.19
566.71
579.06
592.25
606.27
621.12
636.81
653.33
670.68
688.87
707.89

26

J. Pauly et al. / Fuel 137 (2014) 2127

840
790
790

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

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

690
590
490
390
290
240

740
690
640
590

260

280

300

320

340

360

380

540
260

400

280

300

320

Melng point

van Bommel et al.

MeC18:0

Fig. 5. Molar heat capacities versus temperature of the methyl stearate (MeC18:0).

360

380

400

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

axes as already mentioned in this work.
The molar heat capacities of the unsaturated pure FAMEs are
separately presented as these components do not exhibit melting
point in the range of temperature corresponding to our study. The
values are then reported in Table 6 but they cannot be compared
as no data on large range of temperature are available in the literature for these pure components. Even if the results are closed, the
heat capacity of unsaturated FAMEs decreases with the degree of
unsaturation as shown in Fig. 6. The heat capacity trend for unsaturated esters does not show a sharp deviation from the trend of the
saturated esters. But if we consider a constant temperature value, a
nonlinear decrease of the heat capacity is observed as the number
of double bonds in the molecule increases. A completely different
curve was observed as the degree of unsaturation progressed leading to 5.11% difference between the MeC18:0 and MeC18:1 (based
on MeC18:0), 1.16% difference between MeC18:1 and MeC18:2
(based on MeC18:1), and a 1.11% difference between MeC18:2
and MeC18:3 (based on MeC18:2).

MeC18:1

MeC18:2

MeC18:3

MeC20:0

MeC20:1

MeC22:0

MeC22.1

Fig. 6. Liquid molar heat capacity versus temperature for unsaturated FAMEs and
comparison with their degree of unsaturation.

2.2
2.15
2.1

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

Our work

340

T (K)

T (K)

2.05
2
Calculaon

1.95

Experimental

1.9
1.85
1.8
290

300

310

320

330

340

350

360

370

T (K)
Fig. 7a. Liquid mass heat capacity versus temperature for Rapeseed Biodiesel (BR).

2.2

4.2. Biodiesel systems

2.15
2.1

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

To quantify the effect of variations in oil composition on the

heat capacity prediction, we have tested biodiesels derived from
rapeseed oil, soybean oil and other from various oils with FAMEs
compositions close to those of the rapeseed biodiesel. Considering
biodiesel blend as a nearly ideal system [11], a classical mixing rule
was applied to determine the liquid heat capacity of a real mixture
by using the heat capacity of each pure FAME. We used an

2.05
2
Calculaon

1.95

Experimental

1.9
1.85

Table 6
Liquid molar heat capacity of unsaturated of fatty acid methyl esters as a function of
temperature.
T (K)

270
280
290
300
310
320
330
340
350
360
370
380
390

Liquid molar heat capacity (J mol1 K1)

1.8
290

300

310

320

330

340

350

360

370

T (K)
Fig. 7b. Liquid mass heat capacity versus temperature for Soybean Biodiesel (BS).

MeC18:1

MeC18:2

MeC18:3

MeC20:1

MeC22.1

564.63
572.02
579.76
587.84
596.27
605.05
614.18
623.65
633.47
643.64
654.15
665.01
676.22

556.95
564.95
573.10
581.43
589.92
598.58
607.41
616.40
625.56
634.88
644.37
654.03
663.85

552.78
560.71
568.69
576.74
584.85
593.02
601.25
609.54
617.89
626.30
634.77
643.30
651.89

617.11
629.04
640.45
651.34
661.71
671.57
680.91
689.73
698.04
705.83
713.10
719.85
726.09

698.76
707.34
716.25
725.50
735.08
744.99
755.24
765.83
776.74
787.99
799.58
811.50

arithmetic mole or weight fraction average of the pure component

values even though it neglects any contribution due to enthalpy of
mixing.
Measurements have been made in range of temperature from
300 to 360 K. The results for the four different investigated systems
are given in Figs. 7a7d. They show a comparison between the
experimental mass heat capacity of the biodiesel and the results
from calculation with the arithmetic mixing rule. The slopes of
the curve are correctly described for all the systems as the small
deviations in Figs. 7a and 7c can be assigned to experimental

J. Pauly et al. / Fuel 137 (2014) 2127

2.2

Biodiesels have to be considered as complex mixtures but actually

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

2.15
2.1

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

27

2.05

5. Conclusion

2
Calculaon

1.95

Experimental

1.9
1.85
1.8
290

300

310

320

330

340

350

360

370

T (K)
Fig. 7c. Liquid mass heat capacity versus temperature for biodiesel blend 1 (B1).
2.2

The main goal of this work was to investigate the effect of the
temperature (250390 K) on the heat capacities of various saturated
and unsaturated fatty acid methyl esters. The large range of temperature studied allowed analyze this thermophysical property in both
liquid and solid states. The data were compared with the unique
experimental data from the literature for saturated FAMEs whereas
the values for unsaturated FAMEs constitute a new contribution.
The heat capacities at constant pressure for different biodiesels
were obtained by the same procedure. The comparison of our
results with the calculated values has shown that the use of an ideal mixing rule can be considered as a reasonable rst approximation to estimate this thermodynamic property.

2.15

References

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

2.1
2.05
2
Calculaon

1.95

Experimental

1.9
1.85
1.8
290

300

310

320

330

340

350

360

370

T (K)
Fig. 7d. Liquid mass heat capacity versus temperature for biodiesel blend 2 (B2).

deviations. The absolute average deviation is 0.9% for these 4

biodiesels. The maximum absolute average deviation is obtained
for the biodiesel BS with a value of 1.44%.
All the data indicate that the use of basic mixing rule overestimates the value of the experimental liquid mass heat capacity for
all the systems. The employment of an ideal mixture rule on the
FAMEs also ignores the non-identied species which quantities
are variable for the different biodiesels studied (Table 2). These
results suggest also that the excess properties are probably not
negligible and a quantication of the excess heat capacity has to
be described.
Thereby the use of simple additive rule for the determination of
biodiesel heat capacities seems to give reasonably reliable results.

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