J. Chem.

Thermodynamics 105 (2017) 112–122

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Excess enthalpies of ternary mixtures of (oxygenated additives

+ cycloalkane) in fuels and bio-fuels: (dibutyl ether + 1-propanol
+ cyclohexane), or methylcyclohexane, at T = (298.15 and 313.15) K q
Fatima E.M. Alaoui a,b, Fernando Aguilar a, María Jesús González-Fernández a, Eduardo A. Montero a,⇑
a
Departamento de Ingeniería Electromecánica, Escuela Politécnica Superior, Universidad de Burgos, E-09006 Burgos, Spain
b
Ecole Nationale des Sciences Appliquées d’El Jadida, Université Chouaib Doukkali-El Jadida, B.P. 1166, 24002 El Jadida Plateau, Morocco

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

Article history: New experimental excess molar enthalpy data of the ternary systems (dibutyl ether + 1-propanol +
Received 5 May 2016 cyclohexane), or methylcyclohexane, and the corresponding binary systems at T = (298.15 and 313.15) K
Received in revised form 7 September 2016 at atmospheric pressure are reported. A quasi-isothermal flow calorimeter has been used to make the
Accepted 4 October 2016
measurements. All the binary and ternary systems show endothermic character at both temperatures.
Available online 5 October 2016
The experimental data for the systems have been fitted using the Redlich–Kister rational equation and
the UNIQUAC model.
Keywords:
Ó 2016 Elsevier Ltd.
Excess enthalpy
Bio-fuels
Dibutyl ether
1-Propanol

1. Introduction properties of the ether + alcohol + hydrocarbon mixtures makes it

Oxygenated compounds as gasoline-blending agents are used to
reduce emissions of new reformulated gasoline, and they have
been the aim of a broad research since several years [1]. Concerns
about greenhouse gas emissions have increased research efforts
into alternatives in bio-based processes. With regard to transport
fuel, it is expected that future production of these biofuels will
be based on processes using either non-food competing biomasses,
or characterised by low CO2 emissions [2]. Oxygenates that can be
produced from biological sources, such as propanols, butanols and
pentanols, have received recently attention because of its potential
to substitute ethanol as the main alcohol additive [3].
This work is part of a series on excess molar enthalpies of mix-
tures ether + alcohol + hydrocarbon. Amongst the hydrocarbons,
linear and branched alkanes, alkenes and aromatics have been con-
sidered in previous works. References [4–10] correspond to mix-
tures with 1-butanol, while references [11,12] refer to 1-propanol.
This work concerns with dibutyl ether (DBE), 1-propanol, and the
DBE + 1-propanol + cyclohexane, or methylcyclohexane mixtures.
The comparison between the influence of the cycloalkane and the
one of the branched cycloalkane structure on the thermodynamic
q
This paper is part of the Doctoral Thesis of F.E.M. Alaoui.
⇑ Corresponding author.
E-mail address: emontero@ubu.es (E.A. Montero).
an interesting research contribution.
New experimental excess molar enthalpy data of the ternary
systems DBE + 1-propanol + cyclohexane, or methylcyclohexane
and the corresponding binary systems at 298.15 K and 313.15 K
at atmospheric pressure are reported in this work. Excess molar
enthalpies have been measured with a quasi-isothermal flow
calorimeter. The experimental data have been fitted using the Red-
lich–Kister rational polynomials [13] and the UNIQUAC model [14].
2. Experimental method
DBE, 1-propanol, cyclohexane and methylcyclohexane, with a
stated mole purity > 99.3%, were purchased from Sigma Aldrich.
Table 1 shows the purity of all reagents, which were checked by
gas chromatography.
A quasi-isothermal flow calorimeter previously described [4]
have been used to measure the excess molar enthalpies (HE). The
liquids are delivered at programmable constant flow rates into
the mixing coil by means of two precision positive displacement
pumps. An a/c resistance bridge measures the temperature of pure
liquids by a calibrated standard PRT-100 inserted in the pump
body, with an overall uncertainty of ±10 mK. A weighing method
is used to calibrate the flow rates. The flow cell is immersed in a
water bath, thermostatted at T = 298.15 K or at T = 313.15 K. The
measured temperature inside the flow cell presents a standard

http://dx.doi.org/10.1016/j.jct.2016.10.005
0021-9614/Ó 2016 Elsevier Ltd.
 F. E.M. Alaoui et al. / J. Chem. Thermodynamics 105 (2017) 112–122 113

Table 1
Purity and related data of chemicals.

Compound Molecular formula Molar Mass (gmol
1) Stated puritya (mol%) CAS number
Dibutyl ether C8H18O 130.2 >99.3 142-96-1
1-Propanol C3H7OH 60.1 >99.9b 71-23-8
Cyclohexane C6H12 84.2 >99.9 110-82-7
Methylcyclohexane C7H14 98.2 >99.9 108-87-2
a
Determined by gas chromatography (GC) by the supplier Sigma-Aldrich.
b
The water content was checked to be less than 0.01% in mass by titration method.

Table 2
Experimental excess molar enthalpies of binary systems cyclohexane + 1-propanol, and methylcyclohexane + 1-propanol at T = 298.15 K and T = 313.15 K at 0.1 MPa.a

x HE x HE x HE x HE
Jmol
1 Jmol
1 Jmol
1 Jmol
1
298.15 K
x cyclohexane + (1
x) 1-propanol
0.0503 91 0.3005 435 0.5504 623 0.8497 530
0.1005 173 0.3503 486 0.6006 637 0.9005 456
0.1499 247 0.4003 531 0.6503 642 0.9502 346
0.2005 316 0.4501 569 0.6995 636
0.2499 378 0.4998 599 0.8005 582
x methylcyclohexane + (1
x) 1-propanol
0.0498 75 0.3005 372 0.5500 559 0.7996 549
0.1005 144 0.3501 419 0.5998 577 0.8495 508
0.1504 207 0.3998 462 0.6497 587 0.9002 446
0.2000 265 0.4503 501 0.6995 587
0.2504 321 0.5004 533 0.7505 574

313.15 K
x cyclohexane + (1
x) 1-propanol
0.0503 107 0.3004 541 0.5502 790 0.8005 750
0.1005 208 0.3502 607 0.6006 810 0.8497 689
0.1499 300 0.4001 666 0.6503 819 0.9005 598
0.2005 388 0.4500 717 0.6994 813 0.9502 459
0.2498 467 0.4997 758 0.7503 791
x methylcyclohexane + (1
x) 1-propanol
0.0498 100 0.3005 515 0.5500 781 0.7996 756
0.1005 195 0.3502 581 0.5999 798 0.8495 702
0.1505 283 0.3998 640 0.6497 810 0.9002 619
0.2000 365 0.4503 694 0.6995 808 0.9499 486
0.2504 443 0.5005 740 0.7505 790
a
Standard uncertainties of pressure, temperature T and mole fractions x are as follows: u(p) = 0.01 MPa, u(T) = 0.05 K, u(x) = 0.0008. The expanded uncertainty (k = 2) for
the excess enthalpy HE is U(HE) = 10 Jmol
1.

Table 3
Summary of parameters for the representation of HE by Eq. (1), for binary systems cyclohexane + 1-propanol and methylcyclohexane + 1-propanol at T = 298.15 K and at
T = 313.15 K.

Parameters Cyclohexane (1) + 1-propanol (2) Methylcyclohexane (1) + 1-propanol (2)

T = 298.15 K
A0
0.9773
0.9720
A1 2398 2132
A2
1249
890.8
A3
220.8
328.9
A4
294.8
296.6
A5 111.5
DAADðjDHE j=HE Þ /% 0.05 0.07
DrmsDHE /Jmol
1 0.3 0.3
DmaxjDHE j /Jmol
1 0.7 0.5
DmaxjDHE j=HE /% 0.2 0.6

T = 313.15 K
A0
0.9717
0.9605
A1 3033 2961
A2
1472
1232
A3
387.4
557.1
A4
246.3
247.3
A5 250.9
DAADðjDHE j=HE Þ /% 0.09 0.19
DrmsDHE /Jmol
1 0.5 1.6
DmaxjDHE j /Jmol
1 0.8 5.3
DmaxjDHE j=HE /% 0.6 0.8
114 F. E.M. Alaoui et al. / J. Chem. Thermodynamics 105 (2017) 112–122

uncertainty u(T) = 0.05 K. Calibration of the calorimeter was per- As deviation parameters to compare the experimental excess
formed periodically, following the procedure described in refer- enthalpy values with those obtained by Eq. (1), we have used the
ence [4], by simulating an exothermic mixing process by a absolute average deviation, DAAD, root-mean-square deviation,
calibration resistor. Then the HE is calculated from differences in Drms, the maximum absolute deviation, DmaxjDHE j , and the
the heating power control. maximum relative deviation, DmaxðjDHE j=HE Þ , which are defined as
The calculated maximum standard uncertainty of mole fraction follows:
is ±0.0008 at equimolar composition. The mole fractions of the  
ndat  E E 
mixtures obtained in the mixing coil are calculated from the volu- 100 X Hexp
Hcalc 
DAAD ¼   ð2Þ
metric flow rates delivered, the molar masses and the densities of ndat i¼1  HEexp 
the pure compounds. Interpolated density data obtained from Rid-
dick et al. [15] for pure liquids are used to correct the density at the 2n  2 31=2
measured temperature of delivery. Estimated densities at Xdat
E E
6 Hexp
Hcalc 7
T = 298.15 K, were 0.7642, 0.7996, 0.7739 and 0.7647 gcm
3 for 6 i 7
the DBE, 1-propanol, cyclohexane and methylcyclohexane, respec- Drms ¼6
6
7
7 ð3Þ
4 ndat
npar 5
tively. When compared to values found in the literature [16–21],
these results of estimated density agree within <0.1%. Mixtures
of different compositions are studied and in this way the depen-  
 
dence of HE on mole fraction can be determined. The expanded DmaxjDHE j ¼ max HEexp
HEcalc  ð4Þ
uncertainty (k = 2) for the excess enthalpies HE is 10 Jmol
1.
0 E E 
1
Hexp
Hcalc 
3. Results and discussion DmaxðjDHE j=HE Þ ¼ max @ A ð5Þ
HEexp
Table 2 presents the experimental excess molar enthalpies for
the binary mixtures cyclohexane + 1-propanol, and methylcyclo- where HEexp, HEcalc, ndat and npar are the values of the experimental and
hexane + 1-propanol at 298.15 K and 313.15 K at atmospheric calculated excess molar enthalpy, the number of experimental data
pressure obtained in this work. and the number of parameters of the model respectively. The degree
The Redlich–Kister equation, given by Eq. (1), was used to fit the of the polynomial expansion of Eq. (1) was optimized using the
HE measurements, in which the Ai coefficients are determined by F-test [22]. Table 3 summarizes the results of data correlation
the unweighted least-squares method. and deviation parameters for the binary systems at 298.15 K and
P 313.15 K. Fig. 1 presents the plot of the experimental and correlated

1 x1  x2 ni¼1 Ai  ðx1
x2 Þi
1
HE =J  mol ¼ ð1Þ data of hydrocarbons + 1-propanol with Eq. (1).
1 þ A0  ðx1
x2 Þ In relation with the binary mixtures, the mixture cyclohexane +
1-propanol presents the maximum endothermic character, with

Fig. 1. Experimental excess molar enthalpies of hydrocarbon + alcohol. At T = 298.15 K: h, cyclohexane (1) + 1-propanol (2); s, methylcyclohexane (1) + 1-propanol (2). At
T = 313.15 K: j, cyclohexane (1) + 1-propanol (2); d, methylcyclohexane (1) + 1-propanol (2).
, calculated values with Eq. (1), using parameters of Table 2 for hydrocarbon
+ 1-propanol.
 F. E.M. Alaoui et al. / J. Chem. Thermodynamics 105 (2017) 112–122 115

Fig. 2. Experimental excess molar enthalpies of cyclohexane + alcohol. At T = 298.15 K: h, cyclohexane (1) + 1-propanol (2), this work; 4, cyclohexane (1) + 1-butanol (2)
from Ref. [6]. At T = 313.15 K: j, cyclohexane (1) + 1-propanol (2), this work; N, cyclohexane (1) + 1-butanol (2) from Ref. [6]. –, calculated values with Eq. (1), using
parameters of Table 2 for cyclohexane + 1-propanol, and parameters from Ref. [9] for cyclohexane + 1-butanol.

Fig. 3. Experimental excess molar enthalpies of methylcyclohexane + alcohol. At T = 298.15 K: s, methylcyclohexane (1) + 1-propanol (2), this work; *, methylcyclohexane
(1) + 1-butanol (2) from Ref. [9]. At T = 313.15 K: d, methylcyclohexane (1) + 1-propanol (2), this work; +, methylcyclohexane (1) + 1-butanol (2) from Ref. [9]. –, calculated
values with Eq. (1), using parameters of Table 2 for methylcyclohexane + 1-propanol, and parameters from Ref. [9] for methylcyclohexane + 1-butanol.
116 F. E.M. Alaoui et al. / J. Chem. Thermodynamics 105 (2017) 112–122

Table 4
Comparison of literature data and our correlation for excess enthalpy of cyclohexane + 1-propanol and methylcyclohexane + 1-propanol mixtures at 298.15 K at atmospheric
pressure. NP corresponds to the number of data points in the composition range.

Reference Year NP T/K AAD/% Reference uncertainty

Cyclohexane + 1-propanol
Belousov et al. [23] 1970 13 298.15 10.4 1%
Nagata and Kazuma [24] 1977 18 298.15 3.7 –
Vesely et al. [25] 1979 25 298.15 3.7 2%
Letcher et al. [26] 1991 12 298.15 4.5 1%
Zhu et al. [27] 1993 20 298.15 6.8 0.5%
Singh et al. [28] 1996 14 298.15 9.1 1%
Methyl cyclohexane + 1-propanol
Vesely et al. [29] 1975 20 298.15 3.0 1%
Letcher and Nevines [30] 1996 10 298.15 9.6 3%

Fig. 4. Comparison of literature data and our correlation (Eq. (1) and parameters of Table 3) for excess enthalpy of hydrocarbon + 1-propanol mixtures at atmospheric
pressure, at 298.15 K: (a) cyclohexane + 1-propanol: (j), Belousov et al. [23]; (h), Nagata and Kazuma [24]; (4), Vesely et al. [25]; (s), Letcher et al. [26]; (+), Zhu et al. [27];
(d), Singh et al. [28]; (b) methylcyclohexane + 1-propanol: (N), Vesely et al. [29]; (r) Letcher and Nevines [30].

values of experimental HE 642 Jmol
1 and 819 Jmol
1 (at x = 0.65)
at T = 298.15 K and T = 313.15 K respectively. For our binary mix-
tures hydrocarbon + 1-propanol, the HE curves are skewed towards
low mole fractions of alcohol, reflecting its strong self-association
character. The endothermic character of the mixture was expected,
as the dispersion forces of the hydrocarbon are weaker than the
chemical forces of the hydrogen bonds in the alkanol. Experimental
HE data show that, for the given 1-propanol, HE (cyclohexane) > HE
(methylcyclohexane). The increase of the temperature enhances
this effect, due to the weakness of the dispersion forces. The lower
endothermic effect for the mixture of 1-propanol with methylcy-
clohexane with respect to cyclohexane results from stronger inter-
actions with methylcyclohexane than with cyclohexane. The
methyl group of methylcyclohexane has an inductive effect for
stronger interactions and at the same time reduces considerably
the well know stacking organization of cyclohexane molecules.
Comparison of the experimental and correlated data of hydro-
carbon + 1-propanol of this work with the respective hydrocar-
bon + 1-butanol mixtures previously published [4,9] are shown in
Figs. 2 and 3. The mixing effect of the hydrocarbon with the longer
chain of 1-butanol with respect to 1-propanol leads to similar val-
ues of HE, being the increase of the endothermic effect almost the
same with the increase of temperature for both alcohols.
Excess molar enthalpy data for the same binary systems at
298.15 K were found in the literature [23–30], as presented in
Table 4 and Fig. 4. Absolute average differences DAAD between
experimental HE literature data and calculated HE data with our
correlations at the same composition and temperature were found
to be less than 10.4% in all cases. Fig. 4 shows that the highest devi-
ations between our correlation and literature data occur at low
mole fraction of alcohol. The absolute average differences present
a mean value of 4.5% and 5.4% for the mixtures cyclohexane + 1-
propanol and methylcyclohexane + 1-propanol, respectively, when
the middle range of composition, x1 = (0.2–0.8), is considered. No
data for the same mixtures were found at 313.15 K for comparison.
The ternary mixtures DBE (1) + hydrocarbon (2) + 1-propanol
(3) were formed by adding the hydrocarbon (2) to binary mixtures
of fixed composition of DBE (1) + 1-propanol (3). Four values of the
 F. E.M. Alaoui et al. / J. Chem. Thermodynamics 105 (2017) 112–122 117

Table 5
Experimental excess molar enthalpies HE2+13 at 298.15 K at 0.1 MPaa for the addition of hydrocarbon (cyclohexane, or methylcyclohexane), to (DBE (1) + 1-propanol (3)) to form x1
DBE + x2 hydrocarbon + (1
x1
x2) 1-propanol, and values of HE123 calculated from Eq. (6), using the smooth representation of HE13 by Redlich–Kister Eq. (1) with parameters
given in Table 7.

x2 HE2+13/Jmol
1 HE123/Jmol
1 x2 HE2+13/Jmol
1 HE123/Jmol
1

DBE + cyclohexane + 1-propanol
x1/x3 = 0.2500 HE13/Jmol
1 = 474
0.9495 315 339 0.4998 548 785
0.8996 409 457 0.3998 489 773
0.8504 473 544 0.2998 403 735
0.7997 520 615 0.1999 293 672
0.7004 570 712 0.1002 159 585
0.5997 577 767
x1/x3 = 0.6667 HE13/Jmol
1 = 808
0.9499 278 318 0.4998 489 893
0.8996 364 445 0.4004 437 922
0.8500 421 542 0.3003 360 925
0.8003 462 623 0.2003 262 908
0.7002 507 749 0.1006 141 868
0.6004 514 837
x1/x3 = 1.5005 HE13/Jmol
1 = 948
0.9001 319 414 0.3006 315 978
0.8001 409 598 0.2007 229 986
0.6996 449 734 0.1505 177 982
0.5997 454 833 0.1005 121 973
0.4998 431 905 0.0495 62 963
0.4000 383 952
x1/x3 = 4.0025 HE13/Jmol
1 = 834
0.9000 265 348 0.2997 273 857
0.8002 354 521 0.1998 196 863
0.6997 393 644 0.1508 153 861
0.6003 397 730 0.1002 105 856
0.5000 377 794 0.0495 53 846
0.4003 334 834

DBE + methylcyclohexane + 1-propanol

x1/x3 = 0.2503 HE13/Jmol
1 = 474
0.9004 383 430 0.4998 450 687
0.8506 429 500 0.3996 396 681
0.7997 460 555 0.3000 322 654
0.6999 488 630 0.1997 232 612
0.6001 484 674 0.1003 126 553
x1/x3 = 0.6667 HE13/Jmol
1 = 808
0.9002 323 404 0.5003 369 773
0.8495 358 480 0.4003 325 810
0.8005 380 541 0.2998 265 831
0.7001 399 641 0.2000 192 838
0.6000 394 717 0.1001 103 830
x1/x3 = 1.5000 HE13/Jmol
1 = 948
0.8998 263 358 0.5005 294 767
0.8499 290 432 0.4001 259 827
0.7998 307 497 0.3003 211 874
0.7002 319 603 0.1998 153 911
0.6002 314 693 0.0997 82 935
x1/x3 = 4.0041 HE13/Jmol
1 = 834
0.8981 190 275 0.4951 223 644
0.8475 215 342 0.3946 195 700
0.7969 230 399 0.2952 159 747
0.6959 243 497 0.1969 113 783
0.5952 239 577 0.0977 61 814
a
Standard uncertainties of pressure, temperature T and mole fractions x are as follows: u(p) = 0.01 MPa, u(T) = 0.05 K, u(x) = 0.0008. The expanded uncertainty (k = 2) for
the excess enthalpy HE is U(HE) = 10 Jmol
1.

ratio x1/x3 close to 0.2500, 0.6666, 1.5000 and 4.0000, respectively, The experimental excess molar enthalpies are determined by
were formed as different starting binaries. Tables 5 and 6 list the Eq. (6), using the smooth representation of HE13 by Redlich–Kister,
experimental excess molar enthalpies obtained in this work for Eq. (1):
the ternary mixtures DBE + hydrocarbon + 1-propanol at 298.15 K
HE123 ¼ HE2þ13 þ ð1
x2 ÞHE13 ð6Þ
and 313.15 K at 0.1 MPa, respectively. No data for the same ternary
systems at the same temperatures were found in the literature for The following equation was used to fit the ternary HE
comparison. measurements
118 F. E.M. Alaoui et al. / J. Chem. Thermodynamics 105 (2017) 112–122

Table 6
Experimental excess molar enthalpies HE2+13 at 313.15 K at 0.1 MPaa for the addition of hydrocarbon (cyclohexane, or methylcyclohexane) to (DBE (1) + 1-propanol (3)) to form x1
DBE + x2 hydrocarbon + (1
x1
x2) 1-propanol, and values of HE123 calculated from Eq. (6), using the smooth representation of HE13 by Redlich–Kister Eq. (1) with parameters
given in Table 7.

x2 HE2+13/Jmol
1 HE123/Jmol
1 x2 HE2+13/Jmol
1 HE123/Jmol
1

DBE + cyclohexane + 1-propanol
x1/x3 = 0.2500 HE13/Jmol
1 = 545
0.8998 526 581 0.3998 580 907
0.7999 652 761 0.2998 473 855
0.7005 702 865 0.1999 340 776
0.5997 698 916 0.1506 260 723
0.4998 656 929
x1/x3 = 0.6667 HE13/Jmol
1 = 917
0.8997 459 551 0.4004 499 1049
0.8004 564 747 0.3003 406 1048
0.7003 604 879 0.2003 292 1025
0.6004 602 968 0.1007 148 973
0.4998 564 1023
x1/x3 = 1.5000 HE13/Jmol
1 = 1065
0.9001 388 494 0.4003 423 1061
0.8002 484 697 0.3008 344 1088
0.6999 516 836 0.2008 247 1098
0.6000 513 939 0.1004 127 1085
0.5001 480 1012
x1/x3 = 4.0019 HE13/Jmol
1 = 917
0.8001 386 569 0.4001 347 897
0.6997 421 696 0.2995 280 922
0.6002 421 788 0.1998 195 929
0.4998 394 853 0.1002 101 926

DBE + methylcyclohexane + 1-propanol

x1/x3 = 0.2500 HE13/Jmol
1 = 545
0.9004 529 583 0.4998 603 876
0.8506 592 673 0.4006 525 852
0.7997 631 740 0.3000 423 805
0.6999 664 828 0.2006 304 740
0.6001 654 872 0.1003 165 655
x1/x3 = 0.6667 HE13/Jmol
1 = 917
0.9002 445 537 0.5003 489 947
0.8495 494 632 0.4003 426 976
0.8005 521 704 0.2998 345 987
0.7000 540 815 0.2001 247 980
0.5999 528 895 0.1001 131 956
x1/x3 = 1.5000 HE13/Jmol
1 = 1064
0.8997 356 463 0.5004 383 915
0.8498 395 555 0.4001 333 972
0.7998 416 629 0.3003 270 1015
0.7002 428 747 0.1998 192 1044
0.6001 415 841 0.0997 102 1060
x1/x3 = 4.0000 HE13/Jmol
1 = 916
0.7997 290 474 0.3999 240 790
0.6997 304 579 0.3006 194 836
0.6001 297 664 0.2002 139 873
0.5001 275 734 0.0999 73 899
a
Standard uncertainties of pressure, temperature T and mole fractions x are as follows: u(p) = 0.01 MPa, u(T) = 0.05 K, u(x) = 0.0008. The expanded uncertainty (k = 2) for
the excess enthalpy HE is U(HE) = 10 Jmol
1.

HE123 ¼ HE12 þ HE13 þ HE23 þ x1 x2 x3 DHE123 ð7Þ X

n
#j Duji sji
X
n
j¼1
with HE ¼ q i xi
X
n
i¼1
#j sij
DHE123 ¼ B0 þ B1 x1 þ B2 x2 þ B3 x21 þ B4 x22 þ B 5 x1 x2 þ B6 x31 þ B7 x32
j¼1
ð8Þ
where #i ¼ Pqi xqi x , being qi the molecular surface area, obtained as
where the parameters Bi were determined by the unweighted least- j j j

squares method. Correlation data for HE12 of the mixtures DBE (1)
+ hydrocarbon (2) were taken from our previous work [9], while
the same for the mixture DBE (1) + 1-propanol (3) were taken from
Ref. [11]. Table 7 summarizes both sets of data.
Alternatively, the UNIQUAC model has been used to fit the
molar excess enthalpy, which is given by
the sum of the contributions of the functional groups presents in
the compound. Tables 8 and 9 summarize results of data correlation
for the reported ternary systems.
With respect to the first measured ternary system, DBE (1) +
cyclohexane (2) + 1-propanol (3) at 298.15 K, the root mean square
deviation for the rational equation, Drms, is 26.7 Jmol
1, and the
 F. E.M. Alaoui et al. / J. Chem. Thermodynamics 105 (2017) 112–122 119

Table 7 Table 9
Summary of parameters for the representation of HE by Eq. (1), for binary systems Summary of the data reduction results obtained for the ternary systems DBE (1) +
DBE (1) + 1-propanol (3), DBE (1) + cyclohexane (2) and DBE (1) + methylcyclohexane methylcyclohexane (2) + 1-propanol (3) at 298.15 K and 313.15 K using Eqs. (7) and
(2) at T = 298.15 K and at T = 313.15 K. (8) and the UNIQUAC model.

Parameters DBE (1) + 1- DBE (1) DBE (1) Correlationa DHE123 (Eqs. (7) and (8)) UNIQUAC
propanol (3)a + cyclohexane + methylcyclohexane
T = 298.15 K
(2)b (2)b
B0 10403.0
602.617
T = 298.15 K B1
34549.8 1159.26
A0 0 0 0 B2
12320.3 2249.66
A1 3618 1037.1 378.5 B3 7823.8
585.819
A2 1399
362.2
63.8 B4
74905.6 2597.66
A3 959.3 166.2 20.2 B5 108302.0
841.989
A4 1330
139.2
38.2 B6 32310.0
A5 961.2
29 20.6 B7 120342.0
DAADðjDHE j=HE Þ /% 3.9 5.3
T = 313.15 K
A0 0 0 0 DrmsDHE /Jmol
1 28.1 38.5
A1 4083 962.6 355.5 DmaxjDHE j /Jmol
1 67.6 84.6
A2 1488
344.3
60.0 DmaxjDHE j=HE /% 24.6 19.4
A3 1086 186.5 17.6
A4 1254
152.5
15.8 T = 313.15 K
A5 730.0 B0 10342.0
788.307
B1
28506.8 1576.05
a
Data taken from Ref. [11]. B2
18099.5 2662.53
b
Data taken from Ref. [9]. B3
11321.3
615.362
B4
69318.0 3055.54
B5 116,931
780.601
B6 50051.8
B7 124,732
Table 8 DAADðjDHE j=HE Þ /% 2.5 5.3
Summary of the data reduction results obtained for the ternary systems DBE DrmsDHE /Jmol
1 25.4 49.3
(1) + cyclohexane (2) + 1-propanol (3) at 298.15 K and 313.15 K using Eqs. (7) and (8), DmaxjDHE j /Jmol
1 63.7 106.9
and the UNIQUAC model. DmaxjDHE j=HE /% 13.4 18.5
Correlationa DHE123 (Eqs. (7) and (8)) UNIQUAC a
Equivalence between parameters UNIQUAC B0 = Du12; B1 = Du21; B2 = Du13;
T = 298.15 K B3 = Du31; B4 = Du23; B5 = Du32.
B0 10887.1
494.068
B1
34209.8 1182.81 The ternary mixtures DBE (1) + methylcyclohexane (2) + 1-
B2
19828.6 2468.67
propanol (3) also show an endothermic behavior. The root mean
B3 12263.5
630.541
B4
45938.5 2438.51 square deviation for the rational equation is 28.1 Jmol
1 at
B5 102,180
688.332 298.15 K, and 28.0 Jmol
1 at 313.15 K, while the DAAD are 3.9%
B6 28857.5 and 2.9% for the respective temperatures. For the UNIQUAC model,
B7 94312.6
the respective deviation parameters are 38.5 Jmol
1 at 298.15 K,
DAADðjDHE j=HE Þ /% 3.0 5.8
and 49.3 Jmol
1 at 313.15 K for the Drms, while the DAAD presents
DrmsDHE /Jmol
1 26.7 46.8
DmaxjDHE j /Jmol
1 72.5 117.0
5.3% for both temperatures. The maximum experimental values of
DmaxjDHE j=HE /% 20.8 34.5 HE are 948 Jmol
1 at 298.15 K and 1064 Jmol
1 at 313.15 K.
Contours for constant calculated values of HE123 for DBE (1) +
T = 313.15 K
cyclohexane (2) + 1-propanol (3) and DBE (1) + methylcyclohexane
B0 9754.71
579.244
B1
30862.2 1354.30 (2) + 1-propanol (3) at 298.15 K obtained with Eqs. (7) and (8) are
B2
16109.8 2559.94 presented in Figs. 5 and 6 as an illustration, respectively.
B3 2573.21
612.959 The addition of the cycloalkane to the ether + alkanol mixtures
B4
59329.8 2727.41 leads to the positive contribution to HE associated with the disrup-
B5 108,887
645.240
B6 35953.9
tion of interaction between like molecules. Meanwhile, there exists
B7 108,146 the negative contribution due to the creation of interaction
DAADðjDHE j=HE Þ /% 2.0 4.4 between unlike molecules. In our case, addition of cycloalkane to
DrmsDHE /Jmol
1 23.6 45.2 the DBE + alkanol mixtures, the data from Tables 5 and 6 present
DmaxjDHE j /Jmol
1 62.1 105.5 an endothermic behavior due to the stronger influence of the
DmaxjDHE j=HE /% 10.9 18.2 creation of interaction between unlike molecules. For example,
a
Equivalence between parameters UNIQUAC B0 = Du12; B1 = Du21; B2 = Du13;
the maximum calculated value of HE at for the system DBE
B3 = Du31; B4 = Du23; B5 = Du32. (1) + cyclohexane (2) + 1-propanol (3) at 298.15 K, 1000 Jmol
1,
is given at x1 = 0.4500, x2 = 0.2600 and x3 = 0.2900, as shown in
Fig. 5(a). Results show that the endothermic character of the mix-
ture DBE (1) + cyclohexane (2) + 1-propanol (3) is higher than the
DAAD is 3.0%. The DAAD deviation obtained with UNIQUAC model is one of DBE (1) + methylcyclohexane (2) + 1-propanol (3), probably
slightly higher, 5.8%. This system shows an endothermic behavior due to the stronger interactions induced by the methyl group of
in the range of experimental compositions measured. The maxi- methylcyclohexane. For all the ternary systems, the endothermic
mum experimental value of HE is 986 Jmol
1. At T = 313.15 K, effect is enhanced by the increase of the temperature, due to the
the maximum experimental value of HE reaches 1098 Jmol
1, weakness of the dispersion forces. Similar conclusions with respect
while the root mean square deviation gets 26.2 Jmol
1, and the the influence of the branched methyl group were found for the
DAAD is 2.3%, for the rational equation. Meanwhile, for the addition of aromatic hydrocarbon to the DBE + alkanol mixtures
UNIQUAC model, the DAAD is 4.4% and the Drms is 45.3 Jmol
1. [12].
120 F. E.M. Alaoui et al. / J. Chem. Thermodynamics 105 (2017) 112–122

Fig. 5. Contours for constant values of HE123 for (a) DBE (1) + cyclohexane (2) + 1-propanol (3) and (b) DBE (1) + methylcyclohexane (2) + 1-propanol (3) at 298.15 K. +, maximum
value of HE.
 F. E.M. Alaoui et al. / J. Chem. Thermodynamics 105 (2017) 112–122 121

Fig. 6. Contours for constant values of HE123 for (a) DBE (1) + cyclohexane (2) + 1-propanol (3) and (b) DBE (1) + methylcyclohexane (2) + 1-propanol (3) at 313.15 K. +, maximum
value of HE.
122 F. E.M. Alaoui et al. / J. Chem. Thermodynamics 105 (2017) 112–122
4. Conclusions
Isothermal excess molar enthalpies for the ternary systems
DBE + 1-propanol and cyclohexane, or methylcyclohexane at atmo-
spheric pressure at T = 298.15 K and T = 313.15 K were measured
by means of an isothermal flow calorimeter. The binary cycloalk-
ane + 1-propanol mixtures show endothermic effect and strong
asymmetric HE behavior at the measured temperatures. The tern-
ary systems show positive HE values at the measured tempera-
tures. When referred cycloalkane or branched cycloalkane, the
endothermic character of the mixture is higher for the cycloalkane
(cyclohexane) with respect to a branched cycloalkane such as
methylcyclohexane. For all the ternary systems, the endothermic
effect is enhanced by the increase of the temperature. Intermolec-
ular and association effects involved in these systems have been
discussed. The measured excess molar enthalpies data were well
correlated with a rational equation. When using the UNIQUAC
model for the fitting procedure, it shows only slightly higher devi-
ation parameters then the rational equation.
Acknowledgements
Support for this work came from the Ministerio de Ciencia e
Innovación, Spain, Project ENE2009-14644-C02-02, and from the
Ministerio de Asuntos Exteriores y Cooperación, Spain, Agencia
Española de Cooperación Internacional para el Desarrollo AECID,
Project AP/041072/11.
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JCT 16-354