a r t i c l e
i n f o
Article history:
Received 23 September 2014
Received in revised form 19 January 2015
Accepted 28 January 2015
Available online 29 January 2015
Keywords:
Rapeseed oil biodiesel + ethanol mixtures
Density
Excess molar volume
Thermal expansion coefcient
Excess thermal expansion coefcient
a b s t r a c t
The densities of ten binary mixtures of biodiesel made from rapeseed oil and ethanol have been measured for
eight temperatures within the range between 273.15 K and 333.15 K, using an Anton Paar DMA 4500 M
densimeter. The excess molar volume has been calculated from experimental densities. Variation of mixtures volumes was low, but measurable. It was observed that the excess molar volume was positive for all studied mixtures, due to increased physical interactions between fatty acid methyl esters and ethanol. Density variation
was modeled by polynomial regression and the thermal expansion coefcient, as well as its excess value, were
estimated. The excess molar volume and excess thermal expansion coefcient results were tted to the
RedlichKister type polynomial equation to obtain the regression coefcients and estimate the standard deviations and correlation coefcients between experimental and calculated results.
2015 Elsevier B.V. All rights reserved.
1. Introduction
Population and number of vehicles growth, as well as the acute need
for transportation, associated with scarcity of oil resources bring into
focus the need to nd viable alternatives for partial or total substitution
of fossil fuels for automobiles. Alternative sources of energy for transportation are liquid fuels made from biomass, such as biodiesel and
bioethanol, considered as strong candidates for substituting fossil
fuels. Compared to fossil fuels, biofuels have a number of undeniable advantages: they reduce a country's fossil fuel dependency, they are renewable and environmentally friendly, are carbon neutral, their
production supports emerging markets and expand labor markets in agriculture [1,2].
Biodiesel can be produced from various raw materials, such as vegetable oils, animal fat, and some algae species, [3] while bioethanol is
made from sugar, starch or cellulose [4]. Biodiesel can substitute diesel
fuel, while bioethanol is used as a substitute for petrol.
Biodiesel has a high cetane number, wherefrom reduced solid particle and hydrocarbons emissions, but its volatility, caloric value
and ow properties at low temperatures are inferior to those of diesel
[5,6]. This means that the use of biodiesel at low temperatures can be
problematic. However, ethanol has a low cetane number, is very volatile
and has excellent ow properties at low temperature [5].
An efcient method of solving some drawbacks of biodiesel is blending it with substances which can compensate for their decient
http://dx.doi.org/10.1016/j.molliq.2015.01.048
0167-7322/ 2015 Elsevier B.V. All rights reserved.
96
2. Experimental
Ethanol was provided by S.C. Nordic S.A. Biodiesel was produced
from rapeseed oil by the Research Institute for Analytical Instrumentation from Cluj-Napoca. Ethanol purity is 99.3% w/w. Esters' content of
biodiesel is 97.7% w/w, while water content is 183 mgkg1. From the
two constituents, ten binary mixtures were prepared by weight dosing,
using a Mettler AE 163 type analytical balance with a precision of
1 105 g, consequently the uncertainty in the mole fractions is
5 105.
Sample composition was chosen so that it covered the range of
molar concentration between 0 and 1 with steps of about 0.1. After
mixing, the samples were kept for ten days in dark glass bottles, lled
to 95% of the volume and tightly closed. As expected, no components
separation was observed during this period.
The fatty acid methyl ester (FAME) composition prole of biodiesels
used in this work was determined by gas chromatography with an HP
6890 series gas chromatography system equipped with a ame ionization detector and automated split injector.
Before measuring densities, the samples have been thoroughly
mixed and degassed by using an Elmasonic S 50 R type ultrasonic unit.
Densities of the pure liquids and mixtures were measured at atmospheric pressure and at (273.15, 283.15, 288.15, 293.15, 303.15,
313.15, 323.15 and 333.15) K by using an Anton Paar DMA 4500 M
equipped with vibrating U-tube and provided with automatic viscosity
correction. The maximum value of temperature was limited by the relatively low boiling point of bioethanol.
The precision of measured densities was 1 10 5 gcm 3
and uncertainty of the measurements was estimated to be
5 105 gcm3. The temperature in the measuring cell was regulated with Peltier elements and was measured via two integrated Pt 100
platinum resistance thermometers with a precision of 0.01 K.
Before each series of measurements, the densimeter was calibrated
at atmospheric pressure using double distilled and degassed water
and dried air. The density data for water and dried air were taken
from DMA 4500 M Instruction Manual. The cell for density measurement was washed with solvent at a temperature of 333.15 K and air
dried at a temperature of 363.15 K before each fuel sample. In order to
wet the inner walls of the U-tube, before measurements, 20 cm3 of the
samples was passed through the density cell. The measurement cell
was relled with a fuel sample before every measurement was taken.
In order to ensure maximum accuracy, each measurement was done
three times and average of the three values was calculated.
Table 1
Fatty acid methyl ester concentration proles of RME analyzed by gas chromatography.
Fatty acid methyl ester
CAS number
% w/w
110-42-9
111-82-0
124-10-7
112-39-0
112-61-8
1120-28-1
929-77-1
1120-25-8
112-62-9
2390-09-2
1120-34-9
112-63-0
301-00-8
0.02
0.03
0.82
3.81
1.75
0.56
1.13
0.12
58.41
0.68
0.21
21.25
11.21
2
X
1
1
;
xi Mi i
i1
x jM j;
V=T p ;
Table 2
Coefcients and precision of polynomial regression.
x1
c0/gcm3
104
c1/gcm3T1
107
c2/gcm3T2
102 SD
0
0.12025
0.18657
0.27735
0.41781
0.50609
0.60683
0.71334
0.80786
0.90452
0.95107
1
1.31537
0.31892
0.13282
0.97034
1.40845
1.87967
2.53586
3.41613
4.51692
5.88794
7.35090
8.61472
8.07445
7.56664
7.36064
6.94577
6.78120
6.59032
6.30430
5.91772
5.43407
4.83032
4.11437
3.52179
1.10648
1.09825
1.09423
1.08658
1.08100
1.07694
1.06957
1.05816
1.04371
1.02132
1.00071
0.97548
1.00000
0.99995
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
0.22327
1.04200
0.24597
0.52723
0.45762
0.45660
0.59862
9.85563
1.25498
2.11268
1.56606
2.39012
=T p :
97
c0 c1 T c2 T ;
where /gcm3 is the density, T/K is the temperature, c0, c1 and c2 are
parameters of polynomial regressions.
Constants of Eq. (5) were determined based on experimental data by
polynomial regression, using the least-square method are given in
Table 2.
Table 3
Values of , , VE and E for mixture of x1(ethanol) + (1 x1)RME at temperatures from 273.15 K to 333.15 K and atmospheric pressure.
a/gcm3
103 /K1
VE/cm3mol1
105 E/K1
x1
/gcm3
103 /K1
VE/cm3mol1
105 E/K1
273.15 K
0
0.12025
0.18657
0.27735
0.41781
0.50609
0.89574
0.89395
0.89218
0.88961
0.88626
0.88290
0.82121
0.82694
0.83315
0.84035
0.85197
0.86275
0
0.07096
0.09826
0.12027
0.13248
0.12583
0
0.54573
0.77057
1.16260
1.43619
1.52246
0.60683
0.71334
0.80786
0.90452
0.95107
1
0.87845
0.87103
0.86158
0.84545
0.83348
0.81501
0.87536
0.89365
0.91711
0.95179
0.97545
1.00956
0.10675
0.08579
0.05811
0.03540
0.01453
0
1.49402
1.59513
1.57296
1.20138
0.91701
0
283.15 K
0
0.12025
0.18657
0.27735
0.41781
0.50609
0.88840
0.88656
0.88474
0.88213
0.87870
0.87526
0.82503
0.83311
0.84046
0.84968
0.86250
0.87457
0
0.08210
0.11706
0.13930
0.15840
0.15669
0
0.675261
0.965838
1.32143
1.77708
1.88382
0.60683
0.71334
0.80786
0.90452
0.95107
1
0.87074
0.86322
0.85363
0.83734
0.82527
0.80669
0.88894
0.90965
0.93624
0.97507
1.00297
1.04133
0.13556
0.11000
0.08027
0.04891
0.02266
0
1.87762
1.97374
1.94630
1.52366
1.12466
0
288.15 K
0
0.12025
0.18657
0.27735
0.41781
0.50609
0.88474
0.88287
0.88102
0.87838
0.87490
0.87143
0.82696
0.83623
0.84416
0.85441
0.86786
0.88057
0
0.08978
0.12878
0.15303
0.17684
0.17413
0
0.74128
1.06027
1.53845
1.95083
2.06801
0.60683
0.71334
0.80786
0.90452
0.95107
1
0.86686
0.85928
0.84962
0.83325
0.82112
0.80247
0.89584
0.91780
0.94597
0.98692
1.01699
1.05754
0.15378
0.12569
0.09313
0.05549
0.02648
0
2.13805
2.11172
2.10660
1.79263
1.24560
0
293.15 K
0
0.12025
0.18657
0.27735
0.41781
0.50609
0.88108
0.87918
0.87731
0.87462
0.87111
0.86759
0.82890
0.83938
0.84788
0.85919
0.87325
0.88664
0
0.09664
0.13686
0.16885
0.19172
0.19244
0
0.80750
1.15498
1.67588
2.12509
2.25274
0.60683
0.71334
0.80786
0.90452
0.95107
1
0.86297
0.85533
0.84559
0.82912
0.81692
0.79821
0.90282
0.92603
0.95582
0.99894
1.03121
1.07398
0.17230
0.14097
0.10627
0.06340
0.03175
0
2.32904
2.45027
2.26746
1.92205
1.35687
0
303.15 K
0
0.12025
0.18657
0.27735
0.41781
0.50609
0.87379
0.87180
0.86987
0.86710
0.86348
0.85988
0.83280
0.84575
0.85543
0.86888
0.88423
0.89896
0
0.11818
0.16729
0.20626
0.23753
0.23743
0
0.94228
1.34776
1.95559
2.47978
2.61173
0.60683
0.71334
0.80786
0.90452
0.95107
1
0.85515
0.84737
0.83747
0.82078
0.80843
0.78955
0.91701
0.94279
0.97588
1.02344
1.06023
1.10758
0.21685
0.17842
0.13565
0.08028
0.04199
0
2.75776
2.79421
2.71592
2.12615
1.58334
0
313.15 K
0
0.12025
0.18657
0.27735
0.41781
0.50609
0.86653
0.86443
0.86242
0.85955
0.85583
0.85213
0.83674
0.85223
0.86313
0.87877
0.89542
0.91155
0
0.14705
0.20882
0.25778
0.29117
0.29200
0
1.07915
1.54353
2.13965
2.83999
3.01058
0.60683
0.71334
0.80786
0.90452
0.95107
1
0.84729
0.83935
0.82925
0.81232
0.79978
0.78072
0.93150
0.95994
0.99644
1.04859
1.09008
1.14217
0.26748
0.22093
0.17123
0.09960
0.05523
0
3.18254
3.15428
3.11043
2.43499
1.81333
0
323.15 K
0
0.12025
0.18657
0.27735
0.41781
0.50609
0.85929
0.85707
0.85498
0.85199
0.84816
0.84434
0.84073
0.85880
0.87095
0.88885
0.90684
0.92441
0
0.18001
0.25202
0.31526
0.35063
0.35461
0
1.21820
1.74241
2.52823
3.20592
3.39849
0.60683
0.71334
0.80786
0.90452
0.95107
1
0.83937
0.83126
0.82094
0.80374
0.79099
0.77171
0.94633
0.97750
1.01754
1.07444
1.12078
1.17784
0.32690
0.26919
0.21105
0.12105
0.06954
0
3.51359
3.52071
3.51121
2.74874
2.04698
0
333.15 K
0
0.12025
0.18657
0.27735
0.41781
0.50609
0.85208
0.84971
0.84753
0.84441
0.84045
0.83652
0.84476
0.86549
0.87892
0.89913
0.91851
0.93754
0
0.22085
0.30702
0.38477
0.42383
0.42510
0
1.35391
1.93652
2.70988
3.66307
3.77709
0.60683
0.71334
0.80786
0.90452
0.95107
1
0.83140
0.82310
0.81254
0.79505
0.78205
0.76254
0.96150
0.99549
1.03917
1.10099
1.15239
1.21459
0.39495
0.32452
0.25602
0.14392
0.08610
0
3.90501
3.87738
3.90237
3.05496
2.27502
0
x1
b
a
b
98
Table 4
Coefcients Ai, R and SD of the RedlichKister type equation for VE.
Temperature/K
A0
A1
A2
103 SD
273.15
283.15
288.15
293.15
303.15
313.15
323.15
333.15
0.50137
0.61438
0.68763
0.75839
0.94144
1.15799
1.40518
1.69404
0.20908
0.18363
0.17819
0.16221
0.16760
0.20588
0.23950
0.30746
0.03729
0.06609
0.07408
0.08461
0.11292
0.18997
0.25494
0.34541
0.99923
0.99908
0.99927
0.99955
0.99969
0.99972
0.99970
0.99968
2.11506
2.76221
2.72137
2.33811
2.40308
2.80434
3.52132
4.38648
n
X
"
#
n
n
X
2 X
2 1=2
exptli exptl calci calc =
exptli exptl
calci calc
;
i1
i1
i1
6
SD
"
n
X
#1=2
2
i1
where exptli and calci are the experimental and calculated values, respectively, exptl and calc are the average values of the measured and calculated values, respectively, n is the number of experimental values and
m is the numbers of model parameters.
Variation ratio (/T)p was determined by deriving Eq. (5). The
excess thermal expansion coefcient E can be calculated using the
formula: [24]
X
E
i i
Fig. 1. Plot of the excess molar volume of x1(ethanol) + (1 x1)RME at the local atmospheric pressure against mole fraction of ethanol.
V or x1 x2
p
X
Ak x1 x2 x1 1x1
k0
p
X
Fig. 1 shows excess molar volume variation, while Fig. 2 shows the
variation of excess expansion coefcient by temperature as well as by
molecular concentration of ethanol in the mixture. Symbols represent
calculated values, while solid lines show polynomial variations.
The excess molar volume is positive all along the concentration and
temperature range. The same trend was observed for mixtures of ethanol and pure esters [2527]. The fact that excess molar volume is positive indicates the reduction of intermolecular associations (hydrogen
bonds in ethanol, dipoledipole interactions in methyl esters), the presence of repulsive forces due to the electronic charges of both ethanol
and esters, the declustering of ethanol in the presence of esters, and
the domination of steric hindrance in the ester molecules [27]. This effect is not compensated by a reduction in excess volume due to space redistribution of molecules, facilitated by an important difference of
dimensions between the molecules of the two components.
4. Conclusions
Ak 2x1 1 ;
k0
Table 5
Coefcients Ai, R and SD of the RedlichKister type equation for E.
Temperature/K
104 A0
105 A1
105 A2
104 A3
104 A4
107 SD
273.15
283.15
288.15
293.15
303.15
313.15
323.15
333.15
0.61289
0.75837
0.83252
0.90688
1.05825
1.21197
1.36813
1.52054
1.20749
1.49409
1.64018
1.78669
2.08490
2.38775
2.69541
2.99569
1.69663
2.09933
2.30459
2.51045
2.92946
3.35499
3.78728
4.20914
0.73220
0.90599
0.99457
1.08341
1.26424
1.44788
1.63444
1.81651
0.64908
0.80314
0.88167
0.96042
1.12072
1.28351
1.4489
1.61031
0.99753
0.99880
0.99897
0.99841
0.99858
0.99858
0.99891
0.99879
5.33720
4.84151
4.66189
6.42909
6.89925
7.80613
7.76258
9.06294
coefcient displays similar trends with those of excess molar volume, its
maximum values being slightly different, meaning higher ethanol
concentrations.
References
[1] . Trk, Transport 24 (2009) 26.
[2] I. Barabs, Fuel 109 (2013) 563.
[3] M. Balat, H. Balat, Energy Convers. Manage. 49 (2008) 2727.
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
99