Fluid Phase Equilibria 409 (2016) 92e97

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

Thermodynamics properties, VLE and HE, of the systems 2-pentanol

and cyclohexane or methylbenzene for contributing to the knowledge
of new biofuels

J. Segovia, Jorge Rubio, M. Carmen Martín*
Alejandro Moreau, Jose
TERMOCAL (Thermodynamics and Calibration) Research Group, University of Valladolid, Escuela de Ingenierías Industriales, Paseo del Cauce 59, E-47011
Valladolid, Spain

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

Article history: Accurate experimental data of vapoureliquid equilibria (VLE) and excess enthalpies (HE) are reported for
Received 29 July 2015 the binary systems (2-pentanol þ cyclohexane) and (2-pentanol þ methylbenzene). An isothermal total
Received in revised form pressure cell was used for measuring the VLE at T ¼ 313.15 K. The data were correlated using Margules,
16 September 2015
Wilson, NRTL and UNIQUAC equations. The excess enthalpies were measured at two different temper-
Accepted 17 September 2015
Available online 21 September 2015
atures T ¼ (298.15 and 313.15) K using an isothermal flow calorimeter and were correlated by the Redlich
eKister equation. The binary system 2-pentanol þ methylbenzene exhibits an azeotrope and both sys-
tems present a positive deviation from the ideality. Furthermore, an endothermic behaviour is observed
Keywords:
VLE
when 2-pentanol is mixed with these hydrocarbons.
Excess enthalpies © 2015 Elsevier B.V. All rights reserved.
2-Pentanol
Cyclohexane
Methylbenzene
Biofuels

1. Introduction with the reference hydrocarbons, being the main objectives:

Energy saving is an immediate and economic measure which
takes part of any energy policy since it is the key of sustainability,
fuel supply and competitiveness. As part of the target of the
Directive «20-20-20» [1], European Union has insisted on energy
efficiency with a minimum content of 10% of biofuels in gasoline
and diesel fuels.
Thermodynamic properties of biofuels are in general different
from fossil fuels. Moreover, literature data do not have information
about uncertainties and chemical composition lacking on metro-
logical traceability. To facilitate the wider use of biofuels in road
transport, the biofuels and the blends need to become increasingly
compatible with existing logistics as well as future ones; but a good
characterization of the thermodynamic properties is needed to
obtain an in-depth understanding. In the particular case of this
study, it will be performed the characterization of liquid biofuels
* Corresponding author.
E-mail addresses: alejandro.moreau@eii.uva.es (A. Moreau), jose.segovia@eii.
uva.es (J.J. Segovia), jorge.rubio.gallego@alumnos.uva.es (J. Rubio), mcarmen.
martin@eii.uva.es (M.C. Martín).
knowledge of the thermodynamic behaviour of the liquid and
vapour phase (vapour pressure, temperature and phase composi-
tions) of the new liquid fuels, through the measurement of the
vapoureliquid equilibrium of binary mixtures of bioalcohols with
fossil reference hydrocarbons as well as the energy of mixing of the
same mixtures through calorimetric measurements.
The renewable oxygenated additives are mainly alcohols and
ethers, in this case 2-Pentanol can be considered a compound for
second generation of biogasolines due to its high octane rating (up
to 100 Research Octane Number-RON), better water tolerance and
very high heat of combustion.
Continuing with the study of the behaviour of this component,
its mixture with n-heptane or 2,2,4-trimethylpentane was already
published [2], the paper reports accurate experimental data of
vapoureliquid equilibria and excess enthalpies of the mixtures (2-
pentanol þ cyclohexane) and (2-pentanol þ methylbenzene).
In a previous paper [3], binary mixtures with 1-
pentanol þ cyclohexane and 1-pentanol þ methylbenzene were
measured. Both papers will contribute to get a better knowledge of
second generation biofuels, and a comparison of their behaviour is
discussed.

http://dx.doi.org/10.1016/j.fluid.2015.09.035
0378-3812/© 2015 Elsevier B.V. All rights reserved.
 A. Moreau et al. / Fluid Phase Equilibria 409 (2016) 92e97 93

Table 1 Table 3
Material description. VLE data: total pressure, liquid mole fraction and calculated vapour mole fraction
using Margules equation for 2-pentanol (1) þ methylbenzene (2) at T ¼ 313.15 K.a
Chemical name Source Mass fraction purity Purification method
x1 y1,calc p/kPa x1 y1,calc p/kPa
2-Pentanol SigmaeAldrich 0.997 None
Cyclohexane SigmaeAldrich 0.997 None 0.0000 0.0000 7.877 0.5004 0.2053 7.176
Methylbenzene SigmaeAldrich 0.997 None 0.0498 0.0592 8.055 0.5499 0.2207 6.979
0.0995 0.0912 8.042 0.5504 0.2209 6.896
0.1495 0.1122 8.003 0.5999 0.2388 6.743
0.1996 0.1281 7.958 0.6005 0.2390 6.744
2. Experimental section 0.2499 0.1416 7.875 0.6506 0.2604 6.464
0.2998 0.1540 7.780 0.7006 0.2865 6.074
2.1. Materials 0.3497 0.1660 7.628 0.7628 0.3287 5.653
0.3997 0.1782 7.532 0.8008 0.3626 5.255
0.4004 0.1784 7.534 0.8507 0.4223 4.716
The compounds were purchased from SigmaeAldrich and were 0.4498 0.1911 7.355 0.9008 0.5125 4.051
of the highest purity available, chromatography quality reagents 0.4504 0.1913 7.378 0.9509 0.6675 3.268
with a purity >0.99 (GC) for 2-pentanol, >0.995 (GC) for cyclo- 0.4999 0.2051 7.193 1.0000 1.0000 2.302
hexane and >0.998 (GC) for methylbenzene. Their purities were a
Standard uncertainties (k ¼ 1): u(x1) ¼ 0.0005, u(y1,calc) ¼ 0.0005, u(p) ¼ 5 Pa;
also checked by gas chromatography and all were found to be u(T) ¼ 10 mK.
>0.997. The details are summarized in Table 1. The alcohols were
treated with molecular sieve to avoid the water absorption and
analyzed with a KarleFisher test to ensure the low alcohols water ±0.15% (10 mL/min); temperature ±10 mK; the heating and
content. In addition, the pure compounds are degassed using a cooling systems have an stability better than 2.4 mW, and it results
modified distillation method as was detailed in previous papers in an uncertainty of ±0.0001 in the composition of the mixture and
[4,5]. the expanded uncertainty in the excess molar enthalpy is better
than ±1% for a cover factor k ¼ 2 which means a confidence level of
0.95.
2.2. Experimental techniques

An isothermal total pressure cell was used for measuring the 3. Results
vapoureliquid equilibrium of the binary mixtures and it was
described in a previous paper [4,5]. Experimental values were ob- The use of an static technique for measuring the equilibrium
tained in two overlapping runs starting from opposite ends of the means that vapour phase need not be sampled for analysis and data
composition range. The equilibrium properties measured directly are thermodynamically consistent “per se” [7]. Data reduction was
and their standard uncertainties (k ¼ 1) are: injected volume done by Barker's method according to well established procedures
±0.03 mL, temperature ±10 mK and total pressure ±5 Pa. The [8,9]. The non-ideality of the vapour phase was taken into account
overall mole fraction is determined accurately from the volumetric with the virial equation of state, truncated after the second term.
displacement of the injector pistons, the temperature of the in- The pure-component and interaction second virial coefficients (Bii,
jectors and the densities for the pure components. The estimated Bij) were calculated by the Hayden and O'Connell method [10] using
standard uncertainty for mole fractions is ±0.0005. the parameters given by Dymond and Smith [11].
Excess enthalpies were measured with a quasi-isothermal flow VLE data were correlated by the Margules equation up to six-
calorimeter, developed in our laboratory [6]. It is based on the ac- parameter [12]:
curate measurement of the energy required to maintain the mixing
vessel at a constant temperature. To achieve this condition, a Peltier GEm h     i
cooler removes, at constant rate, energy from the flow cell and a ¼ Aji xi þ Aij xj  lji xi þ lij xj xi xj þ hji xi þ hij xj x2i x2j xi xj
RT
control-heater compensates this energy and additionally the en- (1)
ergy liberated (exothermic mixing) or absorbed (endothermic
mixing) by the mixing process. The properties measured directly In addition, Wilson [13], NRTL [14] and UNIQUAC [15] models
and their corresponding standard uncertainties are: flow rate were used for data reduction, whose expressions are given by Eqs.
(2)e(4), respectively:
0 1
Table 2
GEm X X
VLE data: total pressure, liquid mole fraction and calculated vapour mole fraction ¼ xi ln@ xj Aij A (2)
using Margules equation for 2-pentanol (1) þ cyclohexane (2) at T ¼ 313.15 K.a RT
i j
x1 y1,calc p/kPa x1 y1,calc p/kPa
0P 1
0.0000 0.0000 24.575 0.5010 0.0730 20.565 A G x
0.0497 0.0293 24.563 0.5510 0.0790 19.753 GEm X B j ji ji j C
0.1000 0.0377 24.330 0.5511 0.0790 19.765
¼ xi @ P A (3)
RT i
Gki xk
0.1502 0.0421 24.036 0.6008 0.0862 18.832 k
0.2004 0.0460 23.708 0.6013 0.0863 18.834
0.2507 0.0501 23.328 0.6513 0.0953 17.759 0 1
   X   X
0.3006 0.0543 22.899 0.7013 0.1070 16.497
GEm X fi z wi @
X
0.3489 0.0585 22.421 0.7513 0.1225 15.008 ¼ xi ln þ qi xi ln  qi xi ln wj Aji A
0.4007 0.0631 21.879 0.8016 0.1448 13.234 RT xi 2 qi
i i i j
0.4007 0.0631 21.875 0.8513 0.1788 11.140
0.4508 0.0678 21.263 0.9007 0.2391 8.672 (4)
0.4509 0.0678 21.259 0.9498 0.3765 5.820
0.5009 0.0730 20.558 1.0000 1.0000 2.294 where Aij, Aji and a (only for NRTL model) are the adjustable pa-
P P
a
Standard uncertainties (k ¼ 1): u(x1) ¼ 0.0005, u(y1,calc) ¼ 0.0005, u(p) ¼ 5 Pa; rameters, and Gji ¼ exp(ajiAji); wi ¼ qi xi = qj xj ; fi ¼ ri xi = rj xj
u(T) ¼ 10 mK. and z ¼ 10. j j
94 A. Moreau et al. / Fluid Phase Equilibria 409 (2016) 92e97

Table 5
VLE data reduction results: Adjusted parameters, root mean square deviation of
pressure (rms Dp) and the maximum value of the deviation (max jDPj) (Dp is defined
as the difference between the experimental and calculated pressure) for the studied
binary mixtures at T ¼ 313.15 K.

Margules Wilson NRTL UNIQUAC

2-Pentanol (1) þ cyclohexane (2)

A12 2.5113 0.1210 0.6698 1.8150
A21 1.1411 0.7783 1.9306 0.2097
l12 4.4992
l21 0.6424
h12 5.9819
h21 0.8839
a12 0.6372
rms Dp/kPa 0.031 0.137 0.092 0.264
max jDpj=kPa 0.057 0.263 0.194 0.521
2-Pentanol (1) þ methylbenzene (2)
A12 1.7580 0.2385 0.5870 1.7043
A21 1.1453 0.7339 1.3480 0.2829
l12 1.3903
l21 0.7090
h12 1.1377
h21 0.6917
a12 0.6757
rms Dp/kPa 0.018 0.026 0.016 0.040
max jDpj=kPa 0.043 0.062 0.042 0.070
x1,azeotrope 0.0811 0.0787 0.0813
pazeotrope/kPa 8.058 8.036 8.054

Fig. 1. Experimental VLE data at T ¼ 313.15 K for the systems 2-pentanol

▫
(1) þ cyclohexane (2) (D) and 2-pentanol (1) þ methylbenzene (2) ( ). Calculated
values using Margules equation with the parameters given in Table 5 (e).
value of pressure residuals (max jDpj), all these values are given in
Table 5.
Isothermal VLE data, at T ¼ 313.15 K, are reported in Table 2 for Additionally, excess enthalpies were determined at T ¼ (298.15
the binary system (2-pentanol þ cyclohexane) and in Table 3 for (2- and 313.15) K and the measurements are reported in Table 6. A
pentanol þ methylbenzene), where vapour phase mole fractions modified RedlicheKister [16] equation was used for fitting these
were calculated using Margules equation. The same data are shown data:
graphically in Fig. 1. The vapour pressures of the pure compounds
were compared to those published in the literature, as they are
summarized in Table 4 which also contains other data such as E
Hm Xn
Ai ð2x  1Þi1
molar volumes and second virial coefficients for VLE reduction. For 1
¼ xð1  xÞ (5)
J mol i¼1
½1 þ Cð2x  1Þ
correlating the experimental data, minimization of differences
between experimental and calculated pressures was used as Fitting results are summarized in Table 7 which contains the
objective function obtaining the adjustable parameters, the root parameter values, whose number was chosen using F-test [17], and
mean square of pressure residuals (rms Dp) and the maximum the standard deviations.

Table 4
Experimental vapour pressures (psi ), literature values (psi (lit.)) and molar liquid volumes (VLi ) for the pure compounds and the second virial coefficients (Bii, Bij), used for
the calculations, at T ¼ 313.15 K.

2-Pentanol (i ¼ 1) Cyclohexane (i ¼ 2) Methylbenzene (i ¼ 3)

psi /kPa 2.295a 24.572 7.871

psi (lit.)/kPa 2.260b 24.670f 7.880j
2.281c 24.630g 7.861k
2.298d 24.635h 7.897g
2.280e 24.650i 7.894h
VLi /(cm3 mol1)l 111.2 111.08 108.63
Bii/(cm3 mol1)m 2560 1508 2043
Bi1/(cm3 mol1)m 2560 1794 2092
a
Average of 7 runs.
b
Ref. [19].
c
Ref. [20].
d
Ref. [21].
e
Ref. [22].
f
Calculated from Antoine equation using constants reported by Reid et al. [23].
g
Ref. [24].
h
Calculated from Antoine equation using constants reported in Ref. [25].
i
Ref. [26].
j
Ref. [27].
k
Ref. [28].
l
Ref. [29].
m
Calculated by Hayden et al. [10] from Dymond et al. [11].
 A. Moreau et al. / Fluid Phase Equilibria 409 (2016) 92e97 95

Table 6
Experimental excess molar enthalpies HEm as a function of the mole fraction x1 for the
binary systems.a

x1 HEm (J mol1s) x1 HEm (J mol1) x1 HEm (J mol1)

2-Pentanol (1) þ cyclohexane (2) at T ¼ 298.15 K

0.0000 0.0 0.3503 952.3 0.7002 692.8
0.0496 441.3 0.4001 969.1 0.7504 610.1
0.1013 601.2 0.4499 979.7 0.8007 507.0
0.1510 708.0 0.5002 956.0 0.8509 390.1
0.2008 792.1 0.5499 919.8 0.9013 261.4
0.2506 858.1 0.6002 867.9 0.9496 126.4
0.3005 913.7 0.6501 781.0 1.0000 0.0
2-Pentanol (1) þ cyclohexane (2) at T ¼ 313.15 K
0.0000 0.0 0.3502 1107.4 0.7003 828.6
0.0496 556.8 0.4002 1107.5 0.7505 716.8
0.1013 756.7 0.4501 1108.6 0.8007 602.6
0.1510 872.2 0.5001 1085.5 0.8510 460.5
0.2008 959.6 0.5501 1048.8 0.9013 316.3
0.2506 1028.2 0.6001 989.4 0.9496 164.8
0.3003 1078.7 0.6502 918.3 1.0000 0.0
2-Pentanol (1) þ methylbenzene (2) at T ¼ 298.15 K
0.0000 0.0 0.3506 1535.7 0.7010 1224.9
0.0508 624.5 0.4003 1561.8 0.7495 1083.8
0.0998 947.2 0.4501 1562.1 0.8002 921.7
0.1510 1154.5 0.5001 1543.7 0.8509 723.0
0.2002 1296.2 0.5501 1502.3 0.8996 500.5
0.2496 1402.1 0.6003 1441.4 0.9508 249.9
0.3009 1481.0 0.6506 1339.4 1.0000 0.0 Fig. 2. Experimental excess molar enthalpies as a function of the composition for the
2-Pentanol (1) þ methylbenzene (2) at T ¼ 313.15 K binary systems: 2-pentanol (1) þ cyclohexane (2) (◊) at T ¼ 298.15 K and (A) at
0.0000 0.0 0.3506 1708.9 0.7010 1340.6 T ¼ 313.15 K; 2-pentanol (1) þ methylbenzene (2) (D) at T ¼ 298.15 K and (:) at
0.0508 644.0 0.4003 1731.7 0.7495 1179.7 T ¼ 313.15 K. The line represents the values calculated by RedlicheKister equation.
0.0999 1026.6 0.4502 1732.8 0.8002 999.1
0.1510 1282.8 0.5001 1703.2 0.8510 782.1
0.2003 1445.8 0.5502 1649.5 0.8998 550.5 E ¼ 1109 J mol1 and H E ¼ 1733 J mol1 for the systems (2-
0.2496 1567.2 0.6003 1577.2 0.9509 276.5 Hm m
0.3010 1659.5 0.6505 1475.4 1.0000 0.0 pentanol þ cyclohexane) and (2-pentanol þ methylbenzene),
a
Standard uncertainties (k ¼ 1): u(x1) ¼ 0.0001, u(T) ¼ 10 mK, ur(HEm) ¼ 0.5%.
respectively.
At T ¼ 298.15 K and x2-pentanol ¼ 0.45, they decrease to
HmE ¼ 980 J mol1 and H E ¼ 1562 J mol1.
m
4. Discussion Calculated excess functions for the systems under study are
represented in Figs. 3 and 4 at T ¼ 313.15 K. Excess entropies were
Analyzing VLE data reduction, Margules equation leads to the calculated using the relation between them: T$SE ¼ HE  GE since
minimum rms (Dp) ¼ 31 Pa for the mixture with cyclohexane by excess enthalpies were obtained by RedlicheKister and excess
contrast, for the mixture with methylbenzene where the best rms Gibbs energies (GE) by Margules equation.
(Dp) ¼ 16 Pa corresponds to NRTL model, and quite good results are Excess Gibbs energy, whose maximum values are 926 J mol1
obtained for the other models used in the correlations. and 819 J mol1, for the systems (2-pentanol þ cyclohexane) and
As shown in Fig. 1, both mixtures present a positive deviation (2-pentanol þ methylbenzene), respectively, shown again the
from Raoult's law, moreover, the system (2- positive deviation from the ideal behaviour. In addition, they
pentanol þ methylbenzene) presents a maximum pressure azeo- exhibit positive excess entropy in all the composition range since
trope. The azeotrope conditions were calculated with the same the higher positive value of HE being much higher for the binary
models used for data reduction, these values are summarized in mixture (2-pentanol þ methylbenzene).
Table 5 and they are x1 ¼ 0.0813 and p ¼ 8.054 kPa using NRTL A comparison with the systems 1-pentanol þ cyclohexane or
model, which are quite similar to those values obtained using methylbenzene has been carried out. The behaviour of the binary
Margules equation. mixtures presented in this work is different from the observed for
Mixing effect behaviour of these systems results in an endo- the mixtures containing 1-pentanol instead of 2-pentanol already
thermic effect which decreases at lower temperatures, as can be published [3]. First, vapour pressure of the pure compound changes
seen in Fig. 2. increasing from 0.905 kPa for 1-pentanol to 2.295 kPa for 2-
As a consequence, the highest excess enthalpies were at pentanol at T ¼ 313.15 K. Futhermore, the properties of their mix-
T ¼ 313.15 K and a mole fraction of 2-pentanol of 0.45, tures with the same hydrocarbons change, for example, no

Table 7  
 E 
RedlicheKister parameters, standard deviation of excess molar enthalpies, s, and, absolute maximum deviation ðDHm;max Þ for the studied systems.
 
 E 
T (K) A1 A2 A3 A4 A5 C s DHm;max 

(J mol1)

2-Pentanol (1) þ cyclohexane (2)

298.15 3820.33 2353.40 1034.26 442.66 685.90 0.91580 6.3 11.5
313.15 4349.46 2833.91 294.01 359.08 0 0.93901 3.4 7.6
2-Pentanol (1) þ methylbenzene (2)
298.15 6181.67 4049.44 447.30 471.94 247.45 0.84852 4.2 7.0
313.15 6822.29 3390.99 596.13 611.02 0 0.72238 3.4 5.3
96 A. Moreau et al. / Fluid Phase Equilibria 409 (2016) 92e97

Fig. 5. Comparison between the excess entropy for the systems 2-

pentanol þ cyclohexane (e) and 1-pentanol þ cyclohexane (——) at 313.15 K.

Fig. 3. Excess functions for the system 2-pentanol þ cyclohexane at T ¼ 313.15 K: (e)
GEm; (e $$ e) HEm; (——) TSEm.

Fig. 6. Comparison between the excess entropy for the systems 2-

pentanol þ methylbenzene (e) and 1-pentanol þ methylbenzene (——) at 313.15 K.

liquid composition were calculated in order to compare our data

with the literature. The relative root mean square deviations of the
total pressures were around 6%, showing a reasonable good
agreement.

5. Conclusions

Fig. 4. Excess functions for the system 2-pentanol þ methylbenzene at T ¼ 313.15 K: VLE data for both systems show a positive deviation from the
(e) GEm; (e $$ e) HEm; (——) TSEm.
ideal behaviour and a maximum pressure azeotrope is obtained for
the mixture containing methylbenzene. Data reduction using
azeotrope was observed for the mixture (1- Barker's method gives good results for the models Margules, Wil-
pentanol þ methylbenzene) in contrast with the azeotrope son and NRTL.
described for the mixture (2-pentanol þ methylbenzene). The Moreover, excess enthalpies show a strong endothermic
maximum values of excess molar Gibbs energy for the systems with behaviour for both mixtures which increases with temperature and
1-pentanol increase more than 6%, 1006 J mol1 and 870 J mol1, for it is higher for the mixture containing methylbenzene.
the mixtures with cyclohexane and methylbenzene, respectively. The comparison of the behaviour of the alcohols 1-pentanol
However, the maximum values of excess enthalpies decrease 27% versus 2-pentanol shows that no azeotrope is found for the
for the mixtures with 1-pentanol, 817 J mol1 and 1260 J mol1, for mixture (1-pentanol þ methylbenzene) and a lower endothermic
the mixtures with cyclohexane and methylbenzene, respectively. behaviour is obtained when 1-pentanol is mixed with those
As a consequence of this behaviour, excess entropy is negative hydrocarbons.
from 0.15 to 1 for the system (1-pentanol þ cyclohexane). In the
case of the system (1-pentanol þ methylbenzene), excess entropy is Acknowledgements
positive up to 0.92. These effects are plotted in Figs. 5 and 6.
We have found VLE data for the system 2- The authors are grateful for financial support from the Spanish
pentanol þ cyclohexane but at different temperatures [18]. Using Minister de Science and Innovation (MICINN) for Project ENE2009-
the energy parameters of Wilson and NRTL equation, the total 14644-C02-01 and the Project VA391A12-1 of the Junta de Castilla y
pressures, at T ¼ (333.15, 343.15 and 353.15) K, as a function of the
n. Alejandro Moreau thanks the support from European Social
Leo
 A. Moreau et al. / Fluid Phase Equilibria 409 (2016) 92e97 97

n de la Junta de Castilla
Fund (ESF) and from Consejería de Educacio (2014) 89e94.

n. [3] A. Moreau, M.C. Martín, C.R. Chamorro, J.J. Segovia, Fluid Phase Equilib. 317
y Leo
(2012) 127e131.
[4] L.M. Lozano, E.A. Montero, M.C. Martín, M.A. Villaman ~a

n, Fluid Phase Equilib.
Nomenclature 110 (1995) 219e230.
[5] J.J. Segovia, M.C. Martín, C.R. Chamorro, M.A. Villaman ~

an, Fluid Phase Equilib.
133 (1997) 163e172.
Ai adjustable parameters of RedlicheKister equation, Eq. (5) [6] J.J. Segovia, M.C. Martín, D. Vega-Maza, C.R. Chamorro, M.A. Villaman ~a

n,
Aij, Aji adjustable parameters of the VLE correlation models, Eqs. J. Chem. Thermodyn. 41 (2009) 759e763.
(1)e(4) [7] H.C. Van Ness, J. Chem. Thermodyn. 27 (1995) 113e134.
[8] M.M. Abbott, H.C. Van Ness, AIChE J. 21 (1975) 62e71.
Bii, Bij, Bjj second virial coefficients [9] M.M. Abbott, J.K. Floess, G.E. Walsh Jr., H.C. Van Ness, AIChE J. 21 (1975)
C adjustable parameter of RedlicheKister equation, Eq. (5) 72e76.
GEm excess molar Gibbs energy [10] J.G. Hayden, J.P. O'Connell, Ind. Eng. Chem. Process Des. Dev. 14 (1975)
209e216.
HEm excess molar enthalpy [11] J.H. Dymond, E.B. Smith, The Virial Coefficients of Pure Gases and Mixtures e a
i,j constituent identification: 1 or 2 Critical Compilation, Clarendon Press, Oxford, 1980.
lit. literature value [12] B.E. Polling, J.M. Prausnitz, J.P. O'Connell, The Properties of Gases and Liquids,
fifth ed., McGraw-Hill, New York, 2001.
max maximum value of the indicated quantity [13] G.M. Wilson, J. Am. Chem. Soc. 86 (1964) 127e130.
p total pressure [14] H. Renon, J.M. Prausnitz, AIChE J. 14 (1968) 135e144.
psi vapour pressure of pure constituent i [15] D.S. Abrams, J.M. Prausnitz, AIChE J. 21 (1975) 116e128.
[16] O. Redlich, A.T. Kister, Ind. Eng. Chem. 40 (1948) 345e348.
R universal gas constant
[17] S. Wang, H. Cui, J. Multivar. Anal. 117 (2013) 134e149.
rms root mean square [18] P. Gierycz, A. Kosowski, R. Swietlik, J. Chem. Eng. Data 54 (2009) 2996e3001.
SEm excess molar entropy [19] J.M. Rhodes, V.B. Bhethanabotla, S.W. Campbell, J. Chem. Eng. Data 42 (1997)
T absolute temperature 731e734.
[20] D.P. Barton, V.R. Bhethanabotla, S.W. Campbell, J. Chem. Eng. Data 41 (1996)
VLi molar volume of pure liquid i 1138e1140.
x mole fraction, liquid phase [21] J.A. Butler, C.N. Ramchandani, D.W. Thomson, J. Chem. Soc. (1935) 280e285.
y mole fraction, vapour phase [22] L.H. Thomas, R. Meatyard, J. Chem. Soc. (1963) 1986e1995.
[23] R.C. Reid, J.M. Prausnitz, B.E. Poling, The Properties of Gases and Liquids,
McGraw-Hill, New York, 1987.
Greek letters [24] C.R. Chamorro, M.C. Martín, M.A. Villaman ~a

n, J.J. Segovia, Fluid Phase Equilib.
D signifies difference 220 (2004) 105e112.
[25] J.A. Riddick, W.B. Bunger, T.K. Sakano (Eds.), Organic Solvents, Physical
aij adjustable parameter in NRTL model, Eq. (3) Properties and Methods of Purification, Techniques of Chemistry, vol. II,
lij, lji adjustable parameters in Eq. (1) Wiley/Interscience, 1986.
hij, hji adjustable parameters in Eq. (1) [26] C.R. Chamorro, J.J. Segovia, M.C. Martín, E.A. Montero, M.A. Villamana
n, Fluid
Phase Equilib. 156 (1999) 73e87.
[27] E.B. Munday, J.C. Mullins, D.D. Edle, J. Chem. Eng. Data 25 (1980) 191e194.
References [28] D. Ambrose, J. Dalton, Pure Appl. Chem. 61 (1989) 1395e1403.
[29] TRCdThermodynamic Tables of Hydrocarbons and Non Hydrocarbons, Den-
[1] European Union, Energy Efficiency: Delivering the 20% Target, COM, 2008, p. 772. sities, Thermodynamics Research Center, The Texas A&M University System,
~a
[2] A. Moreau, J.J. Segovia, R.M. Villaman
n, M.C. Martín, Fluid Phase Equilib. 384 College Station, 1973.