Fluid Phase Equilibria 425 (2016) 177e182

Contents lists available at ScienceDirect

Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Characterizing second generation biofuels: Excess enthalpies and

vapour-liquid equilibria of the binary mixtures containing 1-pentanol
or 2-pentanol and n-hexane

J. Segovia a, M. Dolores Bermejo b, M. Carmen Martín a, *
Alejandro Moreau a, Jose
a
Research Group Termocal, Thermodynamics and Calibration, University of Valladolid, Escuela de Ingenierías Industriales, Paseo del Cauce 59, E-47011
Valladolid, Spain
b
High Pressure Process Group, Department of Chemical Engineering and Environmental Technology, University of Valladolid, Spain

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

Article history: Experimental data of excess enthalpies and vapour-liquid equilibria (VLE) are reported for the binary
Received 26 April 2016 systems (1-pentanol þ n-hexane) and (2-pentanol þ n-hexane). An isothermal flow calorimeter was
Received in revised form used to determine excess enthalpies at T ¼ (298.15 and 313.15) K and the results were fitted using
27 May 2016
Redlich-Kister equation. Vapour-liquid equilibria data were measured using an isothermal total pressure
Accepted 30 May 2016
Available online 1 June 2016
cell at T ¼ 313.15 K. Barker’s method allows to correlate these data using Margules, Wilson, NRTL and
UNIQUAC equations. An endothermic behavior is observed when 1-pentanol or 2-pentanol is mixed with
n-hexane whose effect increases at higher temperatures and both systems present a positive deviation
Keywords:
VLE
from the Raoult’s law.
Excess enthalpies © 2016 Elsevier B.V. All rights reserved.
1-Pentanol
2-Pentanol
Hexane

1. Introduction equilibria of the mixtures (1-pentanol þ n-hexane) and (2-

pentanol þ n-hexane) are reported.
Energy policies in the European Union focus on the promotion
of the use of biofuels, as is established in Directive «20-20-20» [1], 2. Experimental section
which determines a minimum content of 10% of biofuels overall
gasoline and diesel fuels. 2.1. Materials
Properties of these new biofuels change in comparison with
fossil fuels, therefore a characterization of these properties is 1-Pentanol, 2-pentanol and n-hexane were chromatography
required in order to enhance their use. In this sense, our research quality reagents of the highest purity available from Sigma-Aldrich.
group is involved in the measurement of thermodynamic and Their purities were >0.997 (GC), >0.98 (GC) and >0.99 (GC),
thermophysical properties, such as density, viscosity, heat capacity, respectively and were also checked by gas chromatography being
excess enthalpy or vapour-liquid equilibria, of mixtures of interest better than 0.997. The details are summarized in Table 1.
for the formulation of biofuels.
In this paper, 1-pentanol and 2-pentanol are studied as 2.2. Experimental techniques
oxygenated additives of renewable origin due to their qualities such
as high octane rating or high combustion heat, and n-hexane was Both techniques, used in this work, were described in detail in
chosen as hydrocarbon. Excess enthalpies and vapour-liquid previous papers [2,3] and a brief summary of their main charac-
teristics is reported below.
A quasi-isothermal flow calorimeter, developed in our labora-
tory, was used to determine excess enthalpies [2]. The technique is
* Corresponding author.
E-mail addresses: [email protected] (A. Moreau), jose.segovia@eii.
based on the accurate measurement of the energy required to
uva.es (J.J. Segovia), [email protected] (M.D. Bermejo), mcarmen.martin@eii. maintain the mixing vessel at a constant temperature, using a
uva.es (M.C. Martín). Peltier cooler to remove a constant heat rate from the flow cell, and

http://dx.doi.org/10.1016/j.fluid.2016.05.031
0378-3812/© 2016 Elsevier B.V. All rights reserved.
178 A. Moreau et al. / Fluid Phase Equilibria 425 (2016) 177e182

Table 1
Material description.

Chemical name Source Mass fraction purity (GC)a Purification method

1-Pentanol Sigma-Aldrich 0.997 None

2-Pentanol Sigma-Aldrich 0.997 None
n-Hexane Sigma-Aldrich 0.997 None
a
From the supplier.

a control-heater to compensate this energy and the energy liber- Table 2

ated (exothermic mixing) or absorbed (endothermic mixing) by the Experimental excess molar enthalpies HEm as a function of the mole fraction x1 for the
binary systemsa at atmospheric pressure.
mixing process. The properties measured directly and their corre-
sponding standard uncertainties are: flow rate ±0.15% (10 mL/ x1 HEm/J$mol1 x1 HEm/J$mol1 x1 HEm/
min); temperature ± 10 mK; the heating and cooling systems have a J$mol1

stability better than 2.4 mW. The estimated expanded uncertainties, 1-Pentanol (1) þ n-hexane (2) at T ¼ 298.15 K
for a cover factor k ¼ 2, are: ± 0.0002 in the composition and ±1% in 0.0000 0.3522 0.7015
0.0 537.8 290.1
the excess molar enthalpy.
0.0504 0.4030 0.7514
Vapour-liquid equilibrium measurements were carried out with 329.3 524.2 235.6
an isothermal total pressure cell [3]. The equilibrium properties 0.0999 0.4528 0.8021
measured directly and their standard uncertainties are: injected 413.2 505.8 178.8
volume ±0.03 ml, temperature ±10 mK and total pressure ±5 Pa. 0.1509 0.5035 0.8518
465.6 477.6 126.6
The overall mole fraction is determined accurately from the volu- 0.2010 0.5535 0.9004
metric displacement of the injector pistons, the temperature of the 501.3 441.6 69.6
injectors and the densities for the pure components, obtaining an 0.2524 0.6025 0.9499
estimated standard uncertainty for composition of ±0.0005. 526.9 397.1 21.0
0.3027 0.6525 1.0000
Experimental values were obtained in two overlapping runs start-
533.6 346.3 0.0
ing from opposite ends of the composition range and the repeated 1-Pentanol (1) þ n-hexane (2) at T ¼ 313.15 K
central compositions are used for checking the quality of the 0.0000 0.3503 0.7016
measurements. 0.0 724.5 415.4
0.0504 0.4032 0.7515
455.1 711.6 340.1
0.1000 0.4530 0.8019
3. Results 569.2 688.6 264.8
0.1510 0.5039 0.8517
637.7 652.0 200.0
Excess enthalpies were measured at T¼ (298.15 and 313.15) K for 0.2011 0.5539 0.9004
the binary mixtures (1-pentanol þ n-hexane) and (2-pentanol þ n- 680.1 605.1 128.2
hexane). These data, reported in Table 2 and in Fig. 1, were corre- 0.2525 0.6027 0.9499
lated using a modified Redlich-Kister [4] equation: 705.9 547.3 67.4
0.3007 0.6527 1.0000
720.9 487.4 0.0
E
Hm Xn
Ai ð2x  1Þi1 2-Pentanol (1) þ n-hexane (2) at T ¼ 298.15 K
¼ xð1  xÞ (1)
J$mol1 i¼1
½1 þ Cð2x  1Þ 0.0000 0.0 834.8 637.0
0.3527 0.7018
0.0500 442.7 847.5 546.9
The parameters of equation (1) and the standard deviations are
0.4013 0.7519
given in Table 3. The optimal number of parameters was selected by 0.1016 575.7 848.7 449.7
examining F-test [5]. 0.4530 0.7992
As regards the use of a static technique for measuring VLE, the 0.1523 663.0 835.9 341.3
vapour phase need not be sampled for analysis and the data are 0.5018 0.8509
0.2021 724.9 813.0 229.2
thermodynamically consistent “per se” [6]. Barker’s method [7,8] 0.5518 0.8999
was applied for data reduction and the virial equation of state 0.2509 770.3 769.7 108.9
was used for modelling vapour phase non-ideality. Second virial 0.6027 0.9496
coefficients (Bii, Bij) were calculated by the Hayden and O’Connell 0.3012 808.2 709.8 0.0
0.6528 1.0000
method [9] using the parameters given by Dymond and Smith [10].
2-Pentanol (1) þ n-hexane (2) at T ¼ 313.15 K
The average values of the experimental vapour pressures (Psat
i ) for 0.0000 0.0 1027.2 774.8
the pure compounds and their comparison with the literature [11- 0.3530 0.7019
22], the molar volumes of pure liquids (VLi ) and the second virial 0.0501 559.9 1032.7 670.0
coefficients (Bii, Bij) are indicated in Table 4. 0.4015 0.7519
0.1017 740.8 1028.7 562.8
Margules equation up to six-parameter [23], Wilson [24], NRTL
0.4533 0.7992
[25] and UNIQUAC [26] models were applied for correlating the 0.1524 851.9 1006.4 427.9
experimental data. The expressions are given by Eqs. (2)e(5), 0.5022 0.8509
respectively: 0.2022 923.7 977.5 284.5
0.5521 0.9016

GEm h   i 0.2512 970.7 928.2 133.1

 
¼ Aji xi þ Aij xj  lji xi þ lij xj xi xj þ hji xi þ hij xj x2i x2j xi xj 0.6031 0.9513
RT 0.3014 999.3 855.0 0.0
(2) 0.6531 1.0000
a
Standard uncertainties (k ¼ 1): u(x1) ¼ 0.0001, u(T) ¼ 10 mK, ur(HEm) ¼ 0.5%.
 A. Moreau et al. / Fluid Phase Equilibria 425 (2016) 177e182 179

Table 4
Average values of the experimental vapour pressures (Psi ) for the pure compounds
and literature values (Psi (lit.)), the molar volumes of pure liquids (VLi ) and the second
virial coefficients (Bii, Bij) at T ¼ 313.15 K used for the calculations.

1-Pentanol (i ¼ 1) 2-Pentanol (i ¼ 2) n-Hexane (i ¼ 3)

Psi /(kPa) 0.905a,b

2.295a,b
37.188a
Psi (lit.)/(kPa) 0.918c 2.260e 37.04i
0.872d 2.281f 37.239j
0.891e 2.298g 37.267k
2.280h 37.278l
2.13i 37.283m
VLi /(cm3$mol1)n 110.1 111.2 134.5
Bii/(cm3$mol1)o 3001 2560 1649
Bi3/(cm3$mol1)o 1973 1839 1649
a
Standard uncertainties (k ¼ 1): u(P) ¼ 5 Pa; u(T) ¼ 10 mK.
b
Average of 7 runs.
c
Ref. [11].
d
Ref. [12].
e
Ref. [13].
f
Ref. [14].
g
Ref. [15].
h
Ref. [16].
i
Ref. [17].
j
Ref. [18].
k
Ref. [19].
l
Ref. [20].
m
Calculated from Antoine equation using constants reported by Reid et al. [21].
n
Fig. 1. Experimental excess molar enthalpies as a function of the composition for the Ref. [22].
o
binary systems: 1-pentanol (1) þ n-hexane (2) (◊) at T ¼ 298.15 K and (A) at Calculated by Hayden et al. [9] from Dymond et al. [10].
T ¼ 313.15 K; 2-pentanol (1) þ n-hexane (2) (D) at T ¼ 298.15 K and (:) at
T ¼ 313.15 K. The line represents the values calculated by RedlicheKister equation.

Table 3  
 E 
Parameters of Redlich-Kister Eq. (1), standard deviation of excess molar enthalpies s and, absolute maximum deviation ðDHm;max Þ for the measured systems.
 
T (K) C A1 A2 A3 A4 A5 s  
DHm;max
E


(J$mol1)

1-Pentanol (1) þ n-hexane (2)

298.15 0.97723 1916.52 589.28 973.40 530.06 229.09 3.1 7.4
313.15 0.93272 2619.99 771.12 1194.8 320.09 516.03 2.6 4.2
2-Pentanol (1) þ n-hexane (2)
298.15 0.95900 3352.83 2462.85 289.95 974.04 513.77 2.0 4.0
313.15 0.95612 4040.02 2856.45 132.07 858.56 853.80 2.9 5.2

0 1 have been represented in Fig. 2.

GEm X X Finally, VLE correlation results are summarized in Table 6 which
¼ xi ln@ xj Aij A (3) contains the values of the dimensionless adjustable parameters for
RT
i j the different models, the root mean square of the difference be-
tween experimental and calculated pressures (rms DP) and the
0P 1 maximum value of this difference (max |DP|).
Aji Gji xj
GEm X B j C
¼ xi @ P A (4)
RT i
G x
ki k
k 4. Discussion and conclusions

   X   The study of the energy behavior of these mixtures shows that

GEm X 4 z w
¼ xi ln i þ qi xi ln i both systems have a strong endothermic effect due to the mixing
RT i
x i 2 i
qi process which increases with temperature. The highest excess en-
0 1 (5)
X X thalpies are 724 J mol1 for the system with 1-pentanol at an
 qi xi ln@ wj Aji A alcohol mole fraction of 0.35and 1033 J mol1 for a mole fraction of
i j 2-pentanol of 0.40, both at 313.15 K. The maximum values de-
creases to 528 J mol1 and 849 J mol1 at 298.15 K and mole frac-
where Aij, Aji and a (only for NRTL model) are the adjustable pa- tions of 0.35 and 0.45 for 1-pentanol and 2-pentanol, respectively,
P P
rameters, and Gji ¼ exp(ajiAji);wi ¼ qi xi = qj xj ; 4i ¼ ri xi = rj xj as can be observed in Fig. 1. The higher endothermic behavior of the
and z ¼ 10. j j mixtures with 2-pentanol in comparison with 1-pentanol was also
Table 5 contains the experimental values of total pressure, liquid observed in previous studies [27e31].
phase composition and vapour phase composition, calculated by The four systems are well correlated using modified Redlich-
Margules equation, for the binary systems (1-pentanol or 2- Kister equation with six parameters, and the standard deviations
pentanol and n-hexane at T ¼ 313.15 K, and both sets of data range from 2 to 3.1 J mol1. We have only found data for the system
180 A. Moreau et al. / Fluid Phase Equilibria 425 (2016) 177e182

Table 5 Table 6
Total pressure VLE data, liquid mole fraction and vapour mole fraction calculated VLE correlation results for the binary systems at T ¼ 313.15 K: dimensionless
using Margules equation for the binary systems at T ¼ 313.15 K.a adjustable parameters, root mean square pressure deviation (rms DP) and the
maximum value of the deviation ðmaxjDPjÞ.
x1 y1,calc P(kPa) x1 y1,calc P(kPa)
Margules Wilson NRTL UNIQUAC
1-pentanol (1) þ n-hexane (2)
0.0000 0.0000 37.188 0.5018 0.0204 31.426 1-Pentanol (1) þ n-hexane (2)
0.0287 0.0077 36.627 0.5468 0.0215 30.411 A12 2.8030 0.0948 0.7829 1.7049
0.0813 0.0120 36.210 0.5521 0.0217 30.404 A21 1.3554 0.6109 2.0893 0.2106
0.1338 0.0134 35.774 0.5977 0.0231 29.178 l12 4.7153
0.1857 0.0143 35.310 0.6029 0.0233 29.141 l21 0.6402
0.2380 0.0152 34.807 0.6526 0.0253 27.617 h12 6.3642
0.2899 0.0162 34.271 0.7022 0.0281 25.752 h21 0.9037
0.3416 0.0172 33.692 0.7526 0.0320 23.409 a12 0.5397
0.3931 0.0182 33.040 0.8024 0.0378 20.537 rms DP/kPa 0.070 0.131 0.194 0.452
0.4013 0.0183 33.041 0.8524 0.0473 16.984 max jDPj/kPa 0.137 0.320 0.442 0.954
0.4445 0.0192 32.295 0.9018 0.0659 12.652 2-Pentanol (1) þ n- hexane (2)
0.4516 0.0193 32.289 0.9502 0.1172 7.474 A12 2.5114 0.1473 0.8345 1.7023
0.4957 0.0202 31.431 1.0000 1.0000 0.920 A21 1.3081 0.6580 1.8717 0.2389
2-pentanol (1) þ n-hexane (2) l12 4.2414
0.0000 0.0000 37.188 0.5016 0.0515 30.590 l21 0.6165
0.0497 0.0204 36.773 0.5515 0.0554 29.432 h12 5.4526
0.1005 0.0268 36.315 0.5518 0.0554 29.459 h21 0.6091
0.1504 0.0302 35.805 0.6013 0.0599 28.106 a12 0.6326
0.2008 0.0331 35.258 0.6019 0.0600 28.153 rms DP/kPa 0.045 0.290 0.142 0.500
0.2510 0.0360 34.647 0.6520 0.0657 26.651 max jDPj/kPa 0.088 0.540 0.310 0.926
0.3012 0.0389 33.993 0.7020 0.0729 24.866
0.3513 0.0419 33.273 0.7517 0.0826 22.750
0.4010 0.0449 32.480 0.8018 0.0964 20.176
0.4012 0.0449 32.453 0.8520 0.1185 17.003
0.4514 0.0481 31.557 0.9017 0.1596 13.108
(1-pentanol þ n-hexane) at 298.15 K for comparison, which shown
0.4514 0.0481 31.603 0.9496 0.2594 8.456 some discrepancies between them and with our results. The
0.5014 0.0515 30.574 1.0000 1.0000 2.307 average absolute deviations are 29 J mol1 from [32], 14 J mol1
a
Standard uncertainties (k ¼ 1): u(x1) ¼ 0.0005, u(y1,calc) ¼ 0.0005, u(P) ¼ 5 Pa; from [33], 20 J mol1 from [34] and 12 J mol1 from [35].
u(T) ¼ 10 mK. In addition, the best VLE data correlation is obtained using six-
parameter Margules equation with a root mean square pressure
residual of 70 Pa and a maximum deviation of 137 Pa for the system
(1-pentanol þ n-hexane), and 45 Pa and 88 Pa, respectively for the
system (2-pentanol þ n-hexane). In both systems, the worst fit is
obtained with UNIQUAC model, Wilson adjustment is better than
NRTL for the system with 1-pentanol and the opposite for the
system with 2-pentanol. Pressure versus composition of both
phases behavior is plotted in Fig. 1 where is shown that both sys-
tems exhibit a positive deviation from the ideality but no azeotrope
is found. We have found VLE data for the system 2-pentanol þ n-
hexane at the same conditions [17]. Applying our reduction method
to these data are obtained higher root mean square deviations:
0.372 with six-parameter Margules equation, 0.453 Pa with Wilson
and 0.422 Pa with NRTL. The differences in the pure vapour pres-
sures are also shown in Table 4, where these values are lower than
ours and those reported in the literature. There are isobaric data for
the system 1-pentanol þ hexane [36,37] and isothermal data at
different temperatures [38,39].
Finally, Figs. 3 and 4 represent the calculated excess functions of
the binary systems at 313.15 K, 1-pentanol þ hexane and 2-
pentanol þ hexane, respectively. The excess Gibbs energies were
calculated using the Margules equation, the excess enthalpies were
fitted with the Redlich-Kister equation, and finally the excess en-
tropies were obtained using the relation between them: GE ¼ HE-
T$SE. For the system 1-pentanol þ hexane, the excess Gibbs energy
is higher than the excess enthalpy giving as a result an excess en-
tropy negative in most of the composition range (from x ¼ 0.1 to 1
for 1-pentanol), the maximum GE ¼ 1082 J mol1 at x1 ¼ 0.45.
However, the excess enthalpy is slightly higher than the excess
Gibbs energy obtaining an excess entropy positive in most of the
composition range (from x ¼ 0 to 0.75 for 2-pentanol) for the
system 2-pentanol þ hexane, with a maximum GE ¼ 982 J mol1 at
x1 ¼ 0.45.
Fig. 2. Experimental VLE data at T ¼ 313.15 K for the systems 1-pentanol (1) þ n-
▫
hexane (2) (D) and 2-pentanol (1) þ n-hexane (2) ( ). Calculated values using Mar-
gules equation with the parameters given in Table 6 (─).
 A. Moreau et al. / Fluid Phase Equilibria 425 (2016) 177e182 181

n de la Junta de Castilla
Fund (ESF) and from Consejería de Educacio

n.
y Leo

References

[1] European Union, Energy efficiency: delivering the 20% target, COM (2008)
772.
[2] J.J. Segovia, M.C. Martín, D. Vega-Maza, C.R. Chamorro, M.A. Villaman ~a
n,
J. Chem. Thermodyn. 41 (2009) 759e763.
[3] J.J. Segovia, M.C. Martín, C.R. Chamorro, M.A. Villaman ~
an, Fluid Phase Equilib.
133 (1997) 163e172.
[4] O. Redlich, A.T. Kister, Ind. Eng. Chem. 40 (1948) 345e348.
[5] S. Wang, H. Cui, J. Mult. Anal. 117 (2013) 134e149.
[6] H.C. Van Ness, J. Chem. Thermodyn. 27 (1995) 113e134.
[7] M.M. Abbott, H.C. Van Ness, AIChE J. 21 (1975) 62e71.
[8] M.M. Abbott, J.K. Floess, G.E. Walsh Jr., H.C. Van Ness, AIChE J. 21 (1975)
72e76.
[9] J.G. Hayden, J.P. O
Connell, Ind. Eng. Chem. Process Des. Dev. 14 (1975)
209e216.
[10] J.H. Dymond, E.B. Smith, The Virial Coefficients of Pure Gases and Mixturesea
Critical Compilation, Clarendon Press, Oxford, 1980.
[11] E.B. Munday, J.C. Mullins, D.D. Edle, J. Chem. Eng. Data 25 (1980) 191e194.
[12] D. Ambrose, J. Dalton, Pure Appl. Chem. 61 (1989) 1395e1403.
[13] J.M. Rhodes, V.B. Bhethanabotla, S.W. Campbell, J. Chem. Eng. Data 42 (1997)
731e734.
[14] D.P. Barton, V.R. Bhethanabotla, S.W. Campbell, J. Chem. Eng. Data 41 (1996)
1138e1140.
[15] J.A. Butler, C.N. Ramchandani, D.W. Thomson, J. Chem. Soc. (1935) 280e285.
[16] L.H. Thomas, R. Meatyard, J. Chem. Soc. (1963) 1986e1995.
[17] P. Gierycz, A. Kosowski, R. Swietlik, J. Chem. Eng. Data 55 (2010) 937e940.
[18] TRC, Thermodynamic Tables of Hydrocarbons: Vapor Pressures, Thermody-
Fig. 3. Excess functions for the system 1-pentanol (1) þ n-hexane (2) at T ¼ 313.15 K: namics Research Center, College Station, 1996.
(─) GEm; (─ $$ ─) HEm; (——)TSEm. GEm was calculated using the Margules equation and HEm [19] L.M. Lozano, E.A. Montero, M.C. Martín, M.A. Villaman ~a
n, Fluid Phase Equilib.
with the Redlich-Kister equation. 110 (1995) 219e230.
[20] J. Zielkiewicz, J. Chem. Thermodyn. 23 (1991) 605e612.
[21] R.C. Reid, J.M. Prausnitz, B.E. Poling, The Properties of Gases and Liquids,
McGraw-Hill, New York, 1987.
[22] TRCdThermodynamic Tables of Hydrocarbons and Non Hydrocarbons, Den-
sities, Thermodynamics Research Center, The Texas A&M University System,
College Station, 1973.
[23] B.E. Poling, J.M. Prausnitz, J.P. O’Connell, The Properties of Gases and Liquids,
fifth ed., McGraw-Hill, New York, 2001.
[24] G.M. Wilson, J. Amer, Chem. Soc. 86 (1964) 127e130.
[25] H. Renon, J.M. Prausnitz, AIChE J. 14 (1968) 135e144.
[26] D.S. Abrams, J.M. Prausnitz, AIChE J. 21 (1975) 116e128.
[27] A. Moreau, Thermodynamic Characterization of Environmentally Sustainable
Fuels: Experimental Determination of the Vapor-liquid Equilibrium and the
Excess Enthalpies for Mixtures of Interest to the Development of Biogasolines,
PhD Thesis, University of Valladolid, Spain, 2015.
[28] A. Moreau, M.C. Martín, C.R. Chamorro, J.J. Segovia, Fluid Phase Equilib. 317
(2012) 127e131.
[29] A. Moreau, M.C. Martín, F. Aguilar, J.J. Segovia, Fluid Phase Equilib. 338 (2013)
95e99.
[30] A. Moreau, J.J. Segovia, R.M. Villaman ~
an, M.C. Martín, Fluid Phase Equilib. 384
(2014) 89e94.
[31] A. Moreau, J.J. Segovia, J. Rubio, M.C. Martín, Fluid Phase Equilib. 409 (2016)
92e97.
[32] C. Gonz
alez Posa, L. Nun~ ez, E. Villar, J. Chem. Thermodyn. 4 (1972) 275e281.
[33] T.H. Nguyen, G.A. Ratcliff, J. Chem. Eng. Data 20 (1975) 256e258.
[34] M.M. Pin ~ eiro, B.E. de Cominges, J.L. Legido, M. Lo
pez, M. Mato, M.I. Paz-
Andrade, J. Chem. Themodyn 34 (2002) 961e972.
[35] P.V. Verdes, M.M. Mato, M.I. Paz Andrade, J.L. Legido, J. Chem. Thermodyn. 73
(2014) 224e231.
[36] G. Ovejero, M.D. Romero, E. Diez, T. Lopes, I. Díaz, J. Chem. Eng. Data 52 (2007)
1984e1987.
[37] B. Marrufo, B. Rigby, J. Pla-Franco, S. Loras, J. Chem. Eng. Data 57 (2012)
3721e3729.
[38] S.G. Sayegh, G.A. Ratcliff, J. Chem. Eng. Data 21 (1976) 71e74.
[39] M. Ronc, G.R. Ratcliff, Can. J. Chem. Eng. 54 (1976) 326e332.
Fig. 4. Excess functions for the system 2-pentanol (1) þ n-hexane (2) at T ¼ 313.15 K:
(─) GEm; (─ $$ ─) HEm; (——)TSEm. GEm was calculated using the Margules equation and HEm List of symbols
with the Redlich-Kister equation.
Ai: adjustable parameters of Redlich-Kister equation, Eq. (1)
Aij, Aji: adjustable parameters of the VLE correlation models, Eqs. (2)e(5)
Acknowledgments Bii, Bij, Bjj: second virial coefficients
C: adjustable parameter of Redlich-Kister equation, Eq. (1)
GEm: excess molar Gibbs energy
The authors are grateful for financial support from the Spanish HEm: excess molar enthalpy
Minister de Science and Innovation (MICINN) for Project ENE2009- i,j: constituent identification: 1 or 2
14644-C02-01 and the Project VA391A12-1 of the Junta de Castilla y lit.: literature value
max: maximum value of the indicated quantity

n. Alejandro Moreau thanks the support from European Social
Leo P: total pressure
182 A. Moreau et al. / Fluid Phase Equilibria 425 (2016) 177e182

Psi : vapour pressure of pure constituent i D: signifies difference

R: universal gas constant aij: adjustable parameter in NRTL model, Eq. (4)
rms: root mean square lij, lji: adjustable parameters in six-parameter Margules equation, Eq. (2)
SEm: excess molar entropy hij, hji: adjustable parameters in six-parameter Margules equation, Eq. (2)
T: absolute temperature
VLi : molar volume of pure liquid i ¼ 1, 2
x: mole fraction, liquid phase
y: mole fraction, vapour phase

Greek letters